CN104812466B

CN104812466B - Carbon partition method and system and resulting composition

Info

Publication number: CN104812466B
Application number: CN201380057675.3A
Authority: CN
Inventors: 布伦特·理查德·康斯坦茨; 马克·波维尔尼茨; 雅各布·施耐德; 克里斯·卡米雷
Original assignee: Blue Planet Co Ltd
Current assignee: Blue Planet Systems Corp
Priority date: 2012-09-04
Filing date: 2013-09-04
Publication date: 2018-10-30
Anticipated expiration: 2033-09-04
Also published as: US10711236B2; US20140322803A1; EP2892635A1; JP2015529156A; US20230071790A1; WO2014039578A1; US9714406B2; CA2883816A1; US20230074987A1; CA2883816C; US20140234946A1; JP6329952B2; US20200370001A1; EP2892635A4; US20230054615A1; CN104812466A

Abstract

The aspect of the present invention includes self-contained CO₂Gas remove carbon dioxide (CO₂) method.In some cases, the method includes making to contain CO₂Gas and the aqueous medium of buffered with bicarbonate contact being enough the under conditions of of generating the product rich in bicarbonate radical.When needed, product or its component of the gained rich in bicarbonate radical then can be stored or are further processed, such as be combined with divalent alkaline-earth metal cation being enough the under conditions of of generating solid carbonic acid salt composite.The aspect of the present invention further includes the system for implementation and the product that is generated by the method.

Description

Carbon partition method and system and resulting composition

Cross reference to related applications

The application requires the priority of the following submission date applied according to 35U.S.C. § 119 (e)：On September 4th, 2012 The U.S. Provisional Application No. 61/696,372 of submission；The U.S. Provisional Application No. 61/732,855 that on December 3rd, 2012 submits； The U.S. Provisional Application No. 61/793,512 that on March 15th, 2013 submits；On April 5th, 2013 U.S. Provisional Application No. submitted 61/809,165；The U.S. Provisional Application No. 61/793,585 that on March 15th, 2013 submits；On March 15th, 2013 U.S. submitted State's Provisional Application No. 61/793,731；The U.S. Provisional Application No. 61/807,230 that on April 1st, 2013 submits；May 3 in 2013 The U.S. Provisional Application No. 61/819,427 that day submits；The U.S. Provisional Application No. 61/844,808 that on July 10th, 2013 submits； The U.S. Provisional Application No. 61/866,988 that August in 2013 is submitted on the 16th；And the interim Shen in the U.S. that on July 10th, 2013 submits It please number 61/844,809；The disclosure of the application is hereby incorporated herein by.

Introduction

Carbon dioxide (CO₂) it is a kind of naturally occurring compound being present in gaseous form in the air of the earth.Greatly Gas CO₂Source be different, and be included in respiratory and generate CO₂People and other living organisms and other natural Existing source, such as volcano, hot spring and intermittent spring.

Atmospheric CO₂Other main sources include industrial plant.Many types industrial plant (including cement plant, refining Factory, steel mill and power plant) the various carbon-based fuels of burning, such as fossil fuel and synthesis gas.The fossil fuel of use includes coal, day Right gas, oil, petroleum coke and bio-fuel.Fuel is also derived from Tar sands, oil shale, coal liquid and coal gasification and passes through synthesis Bio-fuel prepared by gas.

CO₂Environment influence have notable importance.CO₂It is generally viewed as a kind of greenhouse gases.Because from the industrial revolution with The mankind's activity come quickly increases Atmospheric CO₂Concentration, institute taking human as CO₂Involved in global warming and climate change and Increase in the magnesium hydrogen salt concentration of ocean.Absorb fossil fuel CO in ocean₂At present just with about 1,000,000 tonnes of CO per hour₂It carries out.

Artificial CO is isolated₂With huge global emergency, and attempting to slow down or reverse global warming and ocean to be acidified Aspect is important.Current carbon trapping and geology partition method have proved to be unpractical, expensive and volume limited potential , and be potential danger.Carbonate mine materialization has been used as that a large amount of CO are sustainably isolated₂(such as with 1,000,000,000 tons of bodies Product meter) most potential method and occur.However, the carbonate mine physicochemical techniques currently developed are in raw material input and energy Challenge in terms of balance has kept the applicability of the method limited.In certain methods, most great limitation is every molar absorbance Carbon dioxide needs two moles of basicity that carbonic acid is made to be converted to carbonate.This method needs to absorption place delivering basicity or leads to The energy intensive technique such as electrochemistry generation sodium hydroxide is crossed to generate basicity.This limitation makes carbonate mine materialization method office Being limited to wherein rare raw material can inexpensively obtain or be hopeful further to develop the minority of the electrochemical techniques to generate basicity Place (Service R.F., " Pave the World！",Science(2012)337:676-678).

Therefore, to developing novel C O₂Isolation technology, which exists, to be given more sustained attention.

It summarizes

The aspect of the present invention includes self-contained CO₂Gas remove carbon dioxide (CO₂) method.In some cases, method Including making to contain CO₂Gas and aqueous medium be enough to remove CO from gas stream₂, and generate the product rich in bicarbonate radical (BRP) it is contacted under conditions of, the product rich in bicarbonate radical may include that the main body of the droplet of phase containing liquid condensation (LCP) is situated between Matter.Products therefrom or its component (such as LCP) can be stored, for being further processed in a variety of applications and/or as needed. The aspect of the present invention further includes the system for implementation and the product that is generated by subject methods.

The aspect of the present invention includes isolation CO₂Method, need the basicity of a little (if any) addition (described in i.e. Method does not need a large amount of basicity or the method is not required to basicity to be added), but generate to CO₂Net isolation.In some sides Face, method generate carbonate mine substance, include the cement with the carbonate mine substance for being applicable in application, such as building road And aggregate, such as described in more detail below；And the CO of purifying₂。

Brief description

Fig. 1 provides the CO of an embodiment according to the present invention₂The general introduction of isolation processes.

Fig. 2 provides the liquid condensation phase that may be present in the product rich in bicarbonate radical generated in the methods of the invention It indicates.

Fig. 3 provides the two teeth complexing Ca in the LCP droplets that may be present in the BRP compositions of the present invention²⁺And HCO₃ ^-Ion It indicates.

Fig. 4 provides the CO of an embodiment according to the present invention₂The schematic depiction of the step of partition method.

Fig. 5 provides the schematic diagram of the single-stage BRLCP reactors of an embodiment according to the present invention.

Fig. 6 provides the schematic diagram of the two-stage BRLCP reactors of an embodiment according to the present invention.

Fig. 7 provides the schematic diagram of the two-stage BRLCP reactors of an embodiment according to the present invention, wherein being further processed The output of reactor is to generate carbonate mine substance.

Fig. 8 provides the schematic diagram of the third-stage reactor of an embodiment according to the present invention.

Fig. 9 and 10 provides the R.O. used in following experimental section the and N.F. schematic diagrames of filtering membrane reactor.

Figure 11 provides the product rich in bicarbonate radical reported in following experimental section such as and generates the figure of the result of scheme.

The amount of the inorganic carbon (DIC) dissolved in the relatively following three different samples of Figure 12：Water, the first CO₂Isolation cement Additive 1 (A1) and the 2nd CO₂Isolation cement additive 2 (A2).

Figure 13 compares with and without the CO of (control) containing isolation₂Mortar cubical sample prepared by the admixture of component Compressive strength.Data are represented with water, CO₂Isolation cement additive 1 (A1) and CO₂Prepared by isolation cement additive 2 (A2) Mortar is tested for cubical 3 days, 7 days and 28 days.

Figure 14 is shown contains CO by addition₂Gas to CO₂It is prepared in the aqueous solution of isolation cement additive 2 (A2) The X-ray diffraction pattern of solid matter.

Figure 15 A and 15B provide the graphical results of the LCP droplet features generated in the embodiment III of following experimental section.

It is described in detail

The aspect of the present invention includes self-contained CO₂Gas remove carbon dioxide (CO₂) method.In some cases, method Including making to contain CO₂Gas stream contacted under conditions of being enough to generate product (BRP) rich in bicarbonate radical with aqueous medium, institute State the bulk media that product may include the droplet of phase containing liquid condensation (LCP).Products therefrom or its component (such as LCP) can be subject to Storage, for being further processed in a variety of applications and/or as needed.The aspect of the present invention further includes being for implementation System and the product generated by subject methods.

Before the more detailed description present invention, it should be understood that the present invention is not limited to the particular embodiment, therefore it is described Embodiment can change certainly.It will also be appreciated that purpose of the term as used herein merely for description particular embodiment, and not It is restrictive to be intended to limitation, because the scope of the present invention will be limited solely by appended claims.

When providing numberical range, it should be understood that unless context in addition clearly stipulate that otherwise the upper limit of that range with It is between lower limit until each interpolation of 1/10th units of lower limit and any other old in the range of that is stated Value or interpolation is stated all to cover within the present invention.These small range of upper and lower bounds can be independently include smaller range In, and be also covered by within the present invention, belong to any boundary clearly excluded in the range of statement.When the range of statement includes When one or two boundary, the range for excluding either one or two of boundary that those include is also included in the present invention.

The numerical value that certain ranges are herein defined as being equipped with term " about " in the past is presented.Term " about " is herein for it Preposition exact numerical and be nearly or approximately that the numerical value of the preposition numerical value of the term provides literal support.In determination When whether numerical value is nearly or approximately the numerical value clearly described, the numerical value not described nearly or approximately can be residing to be presented at it In the case of provide the numerical value clearly described generally equivalence value numerical value.

Unless otherwise defined, otherwise all technical and scientific terms used herein all in this field belonging to the present invention Those of ordinary skill be generally understood with identical meanings.Although can also be used and this paper institutes when implementing or testing the present invention Those of state the method any method similar or equivalent with material and material, but the representative illustrative method of existing description and material.

All announcements and patent are all incorporated herein in its entirety by reference quoted in this specification, the reference Degree just as specifically and individually indicating each individual announcements or patent being herein incorporated by reference generally, and to draw Mode, which is incorporated herein, comes disclosure and description and the relevant method of content and/or material for announcing reference.It quotes any Announcement be all because disclosure of which before the submission date, and should not be construed as approve the present invention due to prior inventions nothing Power is prior to the announcement.Further it is provided that publication date may differ from the practical publication date that may need independently to confirm.

It should be noted that unless context is in addition clearly stipulate that otherwise such as used, singular shape in this paper and appended claims Formula " one " and " described " include a plurality of indicants.It is further noted that claim can be drafted to exclude any optionally to want Element.Therefore, this statement is intended to serve as the removing property term being associated with narration claim elements using such as " unique ", " only " Or the antecedent basis for using " negativity " to limit.

It such as will upon reading this disclosure show and be apparent from for those skilled in the art, each individual implementations described and illustrated herein Scheme have discrete component part and feature, can be easy to the feature of any other several embodiments separate or combine without It departs from the scope of the present invention or spiritual.The sequence for the event that the method for any narration can describe or with logically possible Any other order executes.

Summary

As outlined above, aspect of the invention is related to self-contained CO₂Gas remove CO₂Method.The various implementations of the present invention Scheme is illustrated in Fig. 1, and each component part of wherein Fig. 1 is in following more detail.As shown in fig. 1, it is being enough to generate richness Combination contains CO under conditions of product (BRP) containing bicarbonate radical₂Gas and aqueous medium, the product may include solidifying containing liquid The bulk media of the droplet of rephasing (LCP).Gained can be stored rich in the product of bicarbonate radical, " as it is " for it is a variety of not It in applying, or is further processed, such as applicable product is combined to produce with other materials, be subjected to carbonate deposition condition etc., Wherein gained carbonate deposition can be further used in multi-products again, be used for example as cement to generate the CO of aggregate, purifying₂ Deng.The various aspects of the present invention are now described in more detail below.

Method

The aspect of the present invention includes self-contained CO₂Gas remove CO₂Method.In other words, self-contained CO is provided₂Gas Detach CO₂Method, wherein processing contain CO₂Input gas to generate CO₂Less than the output gas of the input gas.Herein The output gas of the method can be described as " removal CO₂Gas ".Remove CO₂Gas in CO₂Amount be less than contain CO₂'s Input CO present in gas₂Amount remove CO wherein in some cases₂Gas in CO₂Amount ratio contain CO₂Input CO present in gas₂Amount small 95% or smaller, such as 90% or smaller, 85% or smaller, 80% or smaller, 75% or more It is small, 70% or smaller, 65% or smaller, 60% or smaller, 55% or smaller, 50% or smaller, 45% or smaller, 40% or more It is small, 35% or smaller, 30% or smaller, 25% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or more It is small.

In self-contained CO₂Gas remove CO₂When, make described containing CO₂Gas and aqueous medium be enough to generate rich in carbonic acid It is contacted under conditions of the product of hydrogen radical.

Containing CO₂Gas

What is handled in the methods of the invention contains CO₂Gas be include CO₂Gas.Depending on source, contain CO₂Gas Can be pure CO₂Or combined with one or more other gases and/or grain fraction, such as it can be that multicomponent gas is (i.e. multigroup Divide gas stream).Although the CO in the gas₂Amount it is alterable, but in some cases, contain CO₂The pCO that has of gas₂It is 10³Or higher, such as 10⁴Pa or higher, such as 10⁵Pa or higher, including 10⁶Pa or higher.In some cases, contain CO₂Gas In CO₂Amount can be 20,000 or higher, such as 50,000ppm or higher, such as 100,000ppm or higher, including 150, 000ppm or higher, such as 500,000ppm or higher, 750,000ppm or higher, 900,000ppm or higher, until including 1,000,000ppm or higher are (in pure CO₂In exhaust, concentration is 1,000,000ppm).It in some cases, can be 10,000 To 500,000ppm, such as 50,000 to 250,000ppm, including 100, in the range of 000 to 150,000ppm.Containing CO₂Gas Temperature can also change, in some cases, at 0 to 1800 DEG C, such as 100 to 1200 DEG C, and include 600 to 700 DEG C of model In enclosing.

As indicated above, in some cases, contain CO₂Gas be not pure CO₂, because they contain it is one or more its Its gas and/or trace element.It may be present in and contain CO₂Gas in other gases include but not limited to water, nitrogen, single nitrogen oxygen Compound (such as NO, NO₂And NO₃), oxygen, sulphur, single oxysulfide (such as SO, SO₂And SO₃), volatile organic compounds (example Such as benzo (a) pyrene C₂OH₁₂, benzo (g, h, I) C₂₂H₁₂, dibenzo (a, h) anthracene C₂₂H₁₄Deng).It may be present in and contain CO₂Gas In grain fraction include but not limited to the solid being suspended in gas or the particle of liquid, such as heavy metal, as strontium, barium, mercury, Thallium etc..

In certain embodiments, contain CO₂Gas be from industrial plant obtain, such as wherein contain CO₂Gas be to come from The waste feedback material of industrial plant.CO can be contained from its acquisition₂Gas (such as in waste feedback material form from industrial plant) Industrial plant is alterable.Target industrial plant includes but not limited to power plant and industrial products manufactory, such as but is not limited to chemistry With mechanical processing factory, refinery, cement plant, steel mill etc., and CO is generated₂As fuel combustion or other processing steps Other industrial plants of the by-product of (such as the calcining for cement plant).Target waste feedback material includes being generated by industrial plant Gas stream, such as the secondary of the technique executed by industrial plant or with product.

In certain embodiments, it is contemplated that the waste stream generated by the industrial plant of combustion of fossil fuels, described Artificial fuel's product of fossil fuel such as coal, oil, natural gas and naturally occurring organic-fuel deposit such as but is not limited to Tar sands, heavy oil, oil shale etc..In certain embodiments, power plant is to crush coal power generation factory, overcritical coal power generation factory, group Block calcination coal power generation factory, fluidized bed coal power plant, combustion gas or oil burning boiler and steam turbine power generation factory, combustion gas or oil burning boiler are simple Cycle combustion turbine power plant and combustion gas or oil burning boiler combination cycle combustion turbine power plant.In certain embodiments, It is contemplated that the waste stream generated by the power plant of burn synthesis gas, the synthesis gas is i.e. for example, by coal, biomass etc. Gas caused by the gasification of organic substance, wherein in certain embodiments, the factory is integrated gasification combination cycle (IGCC) factory.In certain embodiments, it is contemplated that the waste generated by heat recovery steam generator (HRSG) factory Stream.Target waste stream also includes the waste stream generated by cement plant.The cement plant that waste stream can be used in the method for the present invention includes Shaft furnace or rotary kiln can be used in both wet method factory and dry method factory, the factory, and may include precalcining stove.These types Industrial plant respectively can calcination single-fuel, or can sequentially or concurrently two or more fuel of calcination.Target waste stream is Industrial plant is vented, such as flue gas.For " flue gas ", refer to by calcination fossil or biomass fuel and from then by It is oriented to the gas that the combustion product of chimney (the also referred to as flue of industrial plant) obtains.

Aqueous medium

As outlined above, when implementing method described herein, make to contain CO₂Gas contacted with aqueous medium with self-contained CO₂ Gas remove CO₂.Although the visual performed specified scheme of aqueous medium and change, target aqueous medium include pure water with And including one or more solutes, such as bivalent cation (such as Mg²⁺、Ca²⁺), counter ion (such as carbonate, hydroxyl) etc. Water, wherein aqueous medium can be the aqueous medium of buffered with bicarbonate in some cases.For the carbonic acid in the method for the present invention The aqueous medium of hydrogen salt buffering includes the liquid medium for wherein existing bicarbonate buffer agent.Therefore, target liq aqueous medium CO including dissolving₂, water, carbonic acid (H₂CO₃), bicarbonate ion (HCO₃ ^-), proton (H⁺) and carbanion (CO₃ ^2-).Water The component of bicarbonate buffer agent in property medium is dominated by following equation：

In target aqueous medium, the amount of the different carbonate material compositions in medium can change according to pH.It is low in pH Under about 4.5 some cases, the amount of carbonic acid is 50 to 100%, in the range of 70 to 90%, at pH about 4-9, and bicarbonate The amount of radical ion is 10 to 95%, and in the range of 20 to 90%, and in the case where pH is greater than about 9, the amount of carbanion is 10 To 100%, in the range of 10 to 70%.In some cases, the pH of aqueous medium can 7 to 11, such as 8 to 11, for example, 8 to 10, such as 8 to 9.5, as changed in the range of 8 to 9.3, including 8 to 9.In some cases, pH is 8.2 to 8.7, such as 8.4 to In the range of 8.55.

As needed, aqueous medium can be naturally occurring medium or artificial dielectrics.Naturally occurring buffered with bicarbonate Aqueous medium include but not limited to water from the acquisitions such as sea, ocean, lake, marsh, river mouth, lagoon, brine, alkali lake, inland sea.Carbon The man-made origin of the aqueous medium of sour hydrogen salt buffering can also change, and may include the brine etc. generated by water desalination factory.? Under some cases, it is contemplated that providing the water of excess alkalinity, the excess alkalinity is defined as by addition to bicarbonate ion Source provide basicity.In these cases, the amount of excess alkalinity is alterable, as long as it is enough to provide 1.0 or slightly smaller The basicity equivalence value of (such as 0.9).Target water includes providing 30 or higher, such as 40 or higher, 50 or higher, 60 or more It is high, 70 or higher, 80 or higher, 90 or higher, 100 or those of more high excess alkalinity (milliequivalent/liter).When using institute When stating water, other source of alkalinity, such as NaOH are not needed.

In some cases, with containing CO₂Gas contact aqueous medium be except bicarbonate buffer system (such as above It is described) except, further include the aqueous medium of a certain amount of bivalent cation.It may make in an aqueous medium including bivalent cation The concentration of bicarbonate ion in product rich in bicarbonate radical increases, so that the CO that quantity is much bigger₂To be rich in carbon Bicarbonate ion form in the product of sour hydrogen radical becomes to be isolated.In said case, it is dense to may achieve bicarbonate ion Degree is more than 5,000ppm or higher, such as 10,000ppm or higher, including 15,000ppm or higher.For example, calcium and magnesium point It is not present in seawater under the concentration of 400 and 1200ppm.It is formed by using seawater (or similar water is as aqueous medium) rich Product containing bicarbonate radical, may achieve bicarbonate ion concentration is more than 10,000ppm or higher.

In the embodiment described in which, the variable in the divalent cation source in medium, the divalent cation source can By single divalent cation substance (such as Ca²⁺、Mg²⁺) or two or more different divalent cation substances (such as Ca²⁺、 Mg²⁺Deng) composition, and in some cases, total amount is 1000ppm or higher, such as 2000ppm or higher, including 3000ppm or Higher, such as 5000ppm or higher, including 7500ppm or higher, such as 10,000ppm or higher, such as 15,000ppm or higher, Including 20,000ppm or higher.The target bivalent cation that can be used alone or in combination as divalent cation source includes but not It is limited to：Ca²⁺、Mg²⁺、Be²⁺、Ba²⁺、Sr²⁺、Pb²⁺、Fe²⁺、Hg²⁺Deng.Can be or can not be divalent other target cationic packets It includes but is not limited to：Na⁺,K⁺,NH₄ ⁺And Li⁺And Mn, Ni, Zn, Cu, Ce, La, Al, Y, Nd, Zr, Gd, Dy, Ti, Th, U, La, The cationic substance of Sm, Pr, Co, Cr, Te, Bi, Ge, Ta, As, Nb, W, Mo, V etc..Including divalent or other cationic source, and And the naturally occurring aqueous medium that therefore can be used in the embodiment includes but not limited to：From sea, ocean, river mouth, rush down The aqueous medium of the acquisitions such as lake, brine, alkali lake, inland sea.

Generate the product (BRP) rich in bicarbonate radical

Containing CO₂Gas with the contact of the aqueous medium of buffered with bicarbonate be to be enough self-contained CO₂Gas (i.e. contain CO₂ Gas stream) remove CO₂, and increase the bicarbonate ion concentration of aqueous medium to generate the product rich in bicarbonate radical Under the conditions of carry out.Refer to being characterized in that higher group of the concentration of bicarbonate ion for the product rich in bicarbonate radical Object is closed, wherein in some cases, the concentration of bicarbonate ion can be 5,000ppm or higher, such as 10,000ppm or higher, Including 15,000ppm or higher.In some cases, be rich in bicarbonate radical product in bicarbonate ion 5,000 to 20,000ppm, such as 7,500 to 15,000ppm, including 8, in the range of 000 to 12,000ppm.In some cases, BRLCP In bicarbonate ion total amount can in 0.1wt.% to 30wt.%, such as 3 to 20wt.%, include 10 to 15wt.% model In enclosing.In combination CO₂The pH for the product rich in bicarbonate radical that source and aqueous medium (such as described above) generate afterwards is alterable, And in some cases, 4 to 10, such as 6 to 9, and include in the range of 8 to 8.5.

Product rich in bicarbonate radical can be include single-phase or two or more out of phase liquid compositions.One In a little embodiments, the product rich in bicarbonate radical includes the bulk liquid of the droplet of phase containing liquid condensation (LCP), such as main body Solution.Refer to the phase for the liquid solution for including bicarbonate ion, wherein carbonic acid for " liquid condensation phase " or " LCP " Concentration of the hydrogen radical ion in LCP phases is higher than in surrounding body liquid.

LCP droplets are characterized in that the Liquid precursor phase rich in bicarbonate radical there are meta-stable, wherein bicarbonate radical from Son association is more than the cohesion concentration of bulk solution with the cohesion concentration reached, and is existed with noncrystalline solution state.Referring to Such as Fig. 2.Such as finding, LCP it can contain all groups seen in the bulk solution outside the interface being represented by the dotted line in fig. 2 Point.However, the concentration of bicarbonate ion is higher than in bulk solution.In the case of there is LCP droplets wherein, LCP and Bulk solution can respectively contain ion pair and pre- coring cluster (PNC).When it is present, compared to the ion pair and PNC in solution, from Son is maintained at for a long time in their corresponding phase.Although the number of the droplet in given BRP is alterable, in some cases, deposit In every milliliters of liquid 1 × 10^-6It is a or be more than 1 × 10^-6A droplet, such as per milliliters of liquid 1 × 10^-7A or more droplet, including Per milliliters of liquid 1 × 10^-8A or more droplet, wherein in some cases, the amount of droplet can be per milliliters of liquid 1 × 10^-9 A or more droplet, every milliliters of liquid 1 × 10^-10A or more droplet, every milliliters of liquid 1 × 10^-1It is a or more small Drop or every milliliters of liquid 1 × 10^-12A or more droplet, wherein in some cases, the amount of droplet be every milliliters of liquid 1 × 10^-15A or less droplet, such as per milliliters of liquid 1 × 10^-13A or less droplet, including every milliliters of liquid 1 × 10^-12It is a Or less droplet.

In LCP droplets, such as such as HCO^3-、CO₃ ^2-Deng the equivalent molecule of carbon amount it is alterable, and in some cases, In the range of 1,000 equivalent molecules of carbon of each droplet molecule equivalent to 1,000,000 carbon.Therefore, the carbon equivalent of BRP is dense Degree is alterable, and can easily be used following formula to determine：

(the equivalent molecule amount/droplet of carbon) × (mol/6.022 × 10²³A molecule) × (droplet number/mL) × (1000mL/L)=concentration

In some cases, carbon equivalent concentration is 10nM or higher, as 100nM or higher, 500nM or higher, 750nM or Higher, including 1 micromole or higher, 10 micromoles or higher, 100 micromoles or higher, 500 micromoles or higher, 750 micro- rub You or higher, including 1 mM or higher, such as 10 mMs or higher, wherein in some cases, carbon equivalent concentration be 1M or It is lower, such as 750 mMs or lower, including 500 mMs or lower, such as 250 mMs or lower, for example, 100 mMs or It is lower, 50 mMs or lower, 10 mMs or lower.

In the dual phase composition including LCP droplets, the pH of bulk solution can be higher than the pH of LCP, such as wherein main body stream Body can have in pH 8.0 to pH 9.0, such as the pH in the range of pH 8.2 to pH8.5.Due to the equivalent molecule of carbon in LCP Concentration is higher, so the pH of LCP droplets will be relatively low when compared to the pH of bulk solution, such as the wherein fluid of LCP droplets PH can be in the range of 4.9 to pH 7.8, such as between pH 5.2 and pH 6.8.In these embodiments, pH be not both by The equivalent molecule of carbon in LCP pulls extra protons or acid to balance caused by the charge in LCP.This phenomenon is again so that more CO₂ It is absorbed in bulk solution, thus establishes the cycle of the amount bigger of the LCP in enabling BRP.

Main body phase and LCP are characterized in that thering is different K between each phase_eq, different viscosities and different solubilities.LCP is small Bicarbonate radical, carbonate and the divalent ion component of drop are under proper condition, rear critical nuclei can be gathered into, so as to cause solid phase Those of coring and continued growth.Although bicarbonate ion and such as Ca²⁺Association of the bivalent cation in LCP droplets It is alterable, but in some cases, two tooth bicarbonate ions/divalent cation substance may be present.For example, in target In LCP, Ca may be present²⁺Two tooth substance of/bicarbonate ion, as illustrated in Figure 3.

Although the diameter of the LCP droplets in the main body phase of BRLCP is alterable, in some cases, the diameter of droplet is 1 To 500nm, such as 5 to 25nm, and includes in the range of 10 to 100nm.In some cases, droplet is electrically charged, and Can (in some cases) have in -140 to 120, such as -100 to 40, and include the zeta potential in the range of -40 to -5.? Under some cases, droplet is electrically charged, wherein droplet positively chargeable or negatively charged as needed.Charge is (either just Charge or be negative electrical charge) magnitude it is higher, the stability of LCP droplets can be bigger.In some cases, droplet institute is electrically charged The magnitude of (positive charge or negative electrical charge) is 10 to 100, as in the range of 15 to 75, including 20 to 50, such as 20 to 40.In LCP In droplet, ratio (the i.e. HCO of bicarbonate ion and carbanion₃ ^-/CO₃ ^2-Ratio) it is alterable, and in some cases Under, be 10 or bigger than 1, such as 20 or bigger than 1, including 25 or bigger than 1, such as 50 or bigger than 1.Target LCP's is other Aspect sees Bewernitz etc., " A metastable liquid precursor phase of calcium carbonate And its interactions with polyaspartate, " Faraday Discussions.2012 June 7. DOI:10.1039/c2fd20080e(2012)159:In 291-312.It is true that any suitable scheme can be used for the existence of LCP It is fixed, such as Faatz etc., Advanced Materials, 2004,16,996-1000；Wolf etc., Nanoscale, 2011,3, 1158-1165；Rieger etc., Faraday Discussions, 2007,136,265-277；And Bewernitz etc., Faraday Discussions, the scheme described in 2012,159,291-312.

When the product rich in bicarbonate radical has such as two-phase as described above, bicarbonate ion that the first phase has Concentration can be higher than the second phase, the wherein magnitude difference of bicarbonate ion concentration is alterable, in some cases, 0.1 to 4, in the range of 1 to 2.For example, in some embodiments, the product compositions rich in bicarbonate radical may include first Phase, wherein bicarbonate ion concentration are in the range of 1000ppm to 5000ppm；And second phase, wherein bicarbonate ion Concentration higher, such as wherein concentration is in the range of 5000ppm is to 6000ppm or higher, such as 7000ppm or higher, 8000ppm or higher, 9000ppm or higher, 10,000ppm or higher, 25,000ppm or higher, 50,000ppm or higher, 75,000ppm or higher, 100,000ppm, 500,000 or higher.

BRP and from its generation product (as described in more detail below) may include it is one or more be present in from it generate it Aqueous medium in component, a kind of wherein this or various ingredients can identify the composition from aqueous medium.For example, If aqueous medium is seawater, the authenticating compound packet in BRP compositions (and product from its generation) may be present in It includes but is not limited to：Chlorine root, sodium, sulphur, potassium, bromine root, silicon, strontium etc..Any Identification of The Origin or " label " element are typically with few Amount, such as with 20,000ppm or lower amounts, such as 2000ppm or lower.In certain embodiments, " label " compound is Strontium may be present in the precipitation being incorporated in aragonite lattice, and account for 10,000ppm or lower, in certain embodiments, 3 to 10,000ppm, as in the range of 5 to 5000ppm, including 5 to 1000ppm, such as 5 to 500ppm, including 5 to 100ppm. Another target " label " compound is magnesium, and the amount that can substitute the calcium of up to 20 moles % in carbonate compound exists.Group It closes aqueous medium Identification of The Origin agent visual particular medium source, such as oceanic water, lagoon water, brine of object etc. and changes.At certain In a little embodiments, the calcium carbonate content of precipitation is 25%w/w or higher, such as 40%w/w or higher, and includes 50%w/w Or higher, such as 60%w/w.In certain embodiments, calcium/magnesium ratio that carbonate compound composition has by it from The influence at its water source precipitated, and therefore reflect the water source.In certain embodiments, calcium/magnesium molar ratio 10/1 to 1/5Ca/Mg, in the range of 5/1 to 1/3Ca/Mg.In certain embodiments, carbonate composition is characterized by having The water source for identifying carbonate compound and hydroxide compound ratio, wherein in certain embodiments, this ratio is 100 To 1, such as 10 to 1, and include in the range of 1 to 1.

BRP compositions and can be with being accredited as component with fossil (such as the carbonate of precipitation) from the product of its generation Fuel source, and be therefore accredited as with CO₂The isotope of isolation is composed.For example, in some embodiments, BRP In carbon atom reflection be used to prepare the industrial CO of BRP from its acquisition₂Fossil fuel (such as coal, oil, natural gas, Tar sands) Opposite carbon isotope composition (δ¹³C).Opposite carbon isotope composition (δ with ‰ (permillage) unit¹³C it is) relative to change Petrochemical industry belemnite reference substance (PDB reference substances), two kinds of carbon stable isotopes are (i.e.¹²C and¹³C the measurement of concentration rate).Relative carbon Following equation can be used to calculate in isotopics：

δ¹³C ‰=[(¹³C/¹²C_Sample–¹³C/¹²C_{PDB reference substances})/(¹³C/¹²C_{PDB reference substances})]x 1000

Therefore, the δ of BRP¹³C values serve as CO₂Air source, such as the CO that is discharged by calcination fossil fuel₂Fingerprint.δ¹³C values can Change between source (i.e. fossil fuel source), and in some cases, the δ of BRP¹³C values can be about -3 ‰ to about -45 ‰ Between, wherein δ¹³The negativity of C values is bigger, is more rich in BRP¹²C。(δ¹³C) value can become between source (i.e. fossil fuel source) Change, but in some cases, (the δ of BRP¹³C) value can between -1 ‰ and -50 ‰, between -5 ‰ and -40 ‰, -5 ‰ with - Between 35 ‰, between -7 ‰ and -40 ‰, between -7 ‰ and -35 ‰, between -9 ‰ and -40 ‰ or between -9 ‰ and -35 ‰ In range.In some embodiments, (the δ of BRP¹³C) value be -3 ‰, -5 ‰, -6 ‰, -7 ‰, -8 ‰, -9 ‰, -10 ‰, - 11‰、-12‰、-13‰、-14‰、-15‰、-16‰、-17‰、-18‰、-19‰、-20‰、-21‰、-22‰、- 23‰、-24‰、-25‰、-26‰、-27‰、-28‰、-29‰、-30‰、-31‰、-32‰、-33‰、-34‰、- 35 ‰, -36 ‰, -37 ‰, -38 ‰, -39 ‰, -40 ‰, -41 ‰, -42 ‰, -43., -44 ‰ or -45 ‰ or smaller (i.e. negativity Bigger), wherein (δ¹³C) negativity of value is bigger, is more rich in BRP¹²C.Any appropriate methodology can be used in measuring δ¹³C values, it is described Method includes but not limited to mass spectroscopy or off-axis integrated chamber output spectrum art (off-axis ICOS).

In addition to carbon isotope spectrum analysis or carbon isotope spectrum analysis is substituted, (such as oxygen isotope composes (δ to other isotope spectrums¹⁸O), nitrogen isotope composes (δ¹⁵N), sulfur isotope composes (δ³⁴S) composed with other micro- isotopes) identification is can also be used for for producing It is born from it and obtains the industrial CO of BRP₂The fossil fuel source in source.For example, another target label is (δ¹⁸O).With ‰ The opposite oxygen isotope of (permillage) unit forms (δ¹⁸O) it is averaged oceanic water (VSMOW or SMOW) relative to Vienna standard Reference substance, two kinds of Stability reconstructions are (i.e.¹⁶O and¹⁸O the measurement of concentration rate).Opposite oxygen isotope composition can be used following Equation calculates：

The isolation CO generated as described herein₂Component may originate from the CO of industrial artificial property₂.When combustion of fossil fuel, combustion Burn the CO obtained₂Range is with (δ¹⁸O it) counts.It is being formed in -20 ‰ to -25 ‰ (δ from the oxygen isotope in fossil material¹⁸O model) Enclose interior CO₂When gas, in intake air O₂There are notable oxygen isotopes to be classified for aspect.Although biosphere¹³C signal mainly depends on In plant physiology, in CO₂The vegetable material that activity during intake is consumed with environmental condition and therefore by burning, but CO₂ In δ¹⁸O recycles closely related with water.CO₂The whole world _ δ¹⁸O background signals are by air-ocean CO₂It exchanges to be arranged, and And it is improved in land by interacting with vegetation.Because containing δ¹⁸The molecule of O is characterized in that evaporation rate less than light Molecule (no δ¹⁸O), so they are tended to remain in liquid water, from cloud comparatively fast by rain-out, and therefore in aging cloud Middle reduction.Thus gradient is able to actively maintain, and the gradient shows the δ on cross section¹⁸O isotope autoregression lines subtract to pole It is few, and as upcountry distance increases and reduced above the continent along same latitude.Area differentiation is induced, because of plant Oxygen isotope ratio in the oxygen signal and rain and underground water of water and vegetable material is strongly related.Due to plant physiology process and Classification is coupled with rising, so plant leaf blade water phase is obviously rich in δ compared with source water¹⁸O.Work as CO₂It is again introduced into stomata and blade When without assimilating, CO occurs by being exchanged with the oxygen of the enrichment of plant leaf blade water₂-_δ¹⁸The adjusting of O background signals.Plant During isotope difference in metabolism is happened at carbohydrate and other primary or secondary species biosynthesis；Such as it is opposite In blade water, cellulose oxygen isotope ratio is high by 27 ‰ (± 3 ‰).Caused by other dynamics and balance isotope effect, Secondary species _ δ¹⁸O values reduce；Total plant dry matter has about 18 ‰ δ¹⁸O values.

Since plant has preference in photosynthesis period to being slightly classified this isotope, so being received recently derived from being used as Obtain and the fossil fuel of the plant material of the plant material dried or the organic substance from passing period (such as coal, natural gas, Oil, tar sand oils, propane or other fuel derived from hydrocarbon) it all will be enriched in (δ¹⁸O).However, fuel during use, calcination Exhaust components are (δ¹⁸O) isotopic fractionation, and relative to fossil fuel be reduce, the reason is that be formed in -20 ‰ to - CO in the range of 25 ‰₂When gas, in intake air O₂There are notable oxygen isotopes to be classified for aspect.Work as CO₂Gas is mutual with water phase When effect is to form carbonic acid, bicarbonate ion and carbanion, there are CO₂Oxygen is exchanged with the oxygen in water, and addition comes From the oxygen of water.

Standard the be averaged isotopics of oceanic water (VSMOW or SMOW) in Vienna are defined as discussed rare isotope Mole abundance divided by its most common isotope mole abundance ratio, and be expressed as parts per million (ppm).Citing comes It says,¹⁶O (the most common isotope with eight protons and eight neutrons of oxygen) compares in the seawater¹⁷O (having another neutron) is general All over about 2632 times.The hydrogen and oxygen isotope ratio of VSMOW water are as given a definition：

·²H/¹H=155.76 ± 0.1ppm (ratio of 1 part of about 6420 parts of correspondence)

·³H/¹H=1.85 ± 0.36 × 10^-11Ppm (1 part of correspondence about 5.41 × 10¹⁶The ratio of part, ignores physical property Relevant effect)

·¹⁸O/¹⁶O=2005.20 ± 0.43ppm (ratio of 1 part of about 498.7 parts of correspondence)

¹⁷O/¹⁶O=379.9 ± 1.6ppm (ratio of 1 part of about 2632 parts of correspondence).These compounds will be present in BRP groups In point, and it can measure.Opposite oxygen isotope with ‰ (permillage) unit forms (δ¹⁸O it is) flat relative to Vienna standard Equal oceanic water (VSMOW or SMOW) reference substance, two kinds of Stability reconstruction (i.e. (δ¹⁶) and (δ O¹⁸O the amount of concentration rate)) Degree.Following equation can be used to calculate in opposite oxygen isotope composition：

Therefore, (the δ of BRP¹⁸O) value serves as the CO derived from the fossil fuel release of the organic substance of photosynthetic means by calcination₂ The fingerprint of air source.(δ¹⁸O) value can change between source (i.e. fossil fuel source), and in some cases, (the δ of BRP¹⁸O) value is between about -10 ‰ to about+10 ‰, wherein δ¹⁸The positivity of O values is bigger, and BRP components are more rich in δ¹⁸O。(δ¹⁸O) value can change between source (i.e. fossil fuel source), but in some cases, (the δ of the bicarbonate radical of BRP¹⁸O) value can between -10 ‰ and+9 ‰, between -5 ‰ and+5 ‰, between -5 ‰ and+3 ‰, between -5 ‰ and 4 ‰, -5 ‰ With 3 ‰ between, between -3 ‰ and+4 ‰ or between -2 ‰ and+3 ‰.In some embodiments, bicarbonate adds Add (the δ of the bicarbonate radical of agent¹⁸O) value be -12 ‰, -11 ‰, -10 ‰, -9 ‰, -8 ‰, -7 ‰, -6 ‰, -5 ‰, -4 ‰, - 3‰、-2‰、-1‰、0‰、1‰、2‰、3‰、4‰、5‰、6‰、7‰、8‰、9‰、10‰、11‰、12‰、13‰、 14 ‰, 15 ‰, 16 ‰, 17 ‰, 18 ‰, 19 ‰ or 20 ‰ or bigger, wherein (δ¹⁸O) negativity of value is bigger, bicarbonate component In δ¹⁸The reduction of O is more, the reason is that the classification during burning.Compare the oxygen of aerial oxygen and seawater, air O₂Just¹⁸For O Than seawater enrichment almost 24 ‰, and this enrichment is known as Dorr effect (Dole effect).Therefore, work as CO₂Gas and water phase When interaction is to form carbonic acid, bicarbonate ion and carbonate, there are CO₂Oxygen is exchanged with the oxygen in water, and addition comes from The oxygen of water, and even with exchange, because for the oxygen grade and both Dorr effects caused by combustion of fossil fuels, so being formed Carbonic acid, bicarbonate ion and carbonate oxygen isotope composition will never be as formed the vegetable material of fossil fuel from it Or CO₂The natural water reacted is generally by enrichment.Any appropriate methodology can be used in measuring δ¹⁸O values, the method includes but It is not limited to mass spectroscopy or off-axis integrated chamber output spectrum art (off-axis ICOS).

Deuterium (symbol D or²H, also referred to as heavy hydrogen) it is one of two kinds of hydrogen stable isotopes.The core (being known as deuteron) of deuterium contains one A proton and a neutron, and more conventional hydrogen isotope protium does not have neutron in core.It the earth big midocean it is natural Abundance is corresponding about 1 atom in 6,420 hydrogen.Therefore, deuterium accounts for about the 0.0156% of all naturally occurring hydrogen of big midocean (or it is based on quality：0.0312%), most common isotope (hydrogen -1 or protium) accounts for more than 99.98%.From the day of a type To the natural water of another type, the abundance of deuterium slightly changes (referring to VSMOW) right water.

The measuring method of mass spectrum for Accurate Determining hydrogen-deuterium ratio is developed.Using with (i.e. 6700 parts of " normal abundance " Have 1 part of D in H) substance, it is possible to this ratio is measured in ± 0.10% degree.Operable as little as 0.1mg H₂ (0.001ml H₂O sample).The natural evaporation that oxygen isotope can be made to be classified and condensation, which has been displayed, can also be such that hydrogen isotope is classified. The ratio of the two classification objects is equal in H₂O/H^DO and H₂O¹⁶/H₂O¹⁸Steam pressure ratio between ratio.

The deuterium of oceanic water in the range of 0.0153 to 0.0156 mole of %, and the deuterium of U.S.'s fresh water 0.0133 to In the range of 0.0154 mole of %.This is served as compared to metrical water, by CO₂The bicarbonate radical that interaction with seawater obtains Fingerprint.It occupies under earth's surface or the seawater Chang Jiqi in arid lake is bitter, and be derived from and once occupy continent, and fill with ground The ancient times seawater of the sedimentary basin of ball.Although the isotopics of known oxygen and hydrogen isotope increase with salinity and are changed, poor It is different to be more than the seen anything with salinity altercation.Most of carbonate mine substances also contain a small amount of bicarbonate radical from Son, and therefore there is the hydrogen of the isotope analysis for this fingerprint.

Many trace elements are derived under ancient times seawater and the earth's surface to interact with host rock specific to brine. Trace element is incorporated by being formed with flue gas and these water phase interactions those of in these trace elements and flue gases In bicarbonate, the flue gas and these water give fingerprint to the carbonate and bicarbonate compound of formation.

Due to classification, formation nitrous oxide and other NOx compounds also subtract 15N contents during combustion of fossil fuels It is few, and serve as footprint.Sulfur dioxide also shows the classification behavior in the source of sulphur of the identification from fossil fuel.

Process conditions

As indicated above, make to contain CO₂Gas contacted under conditions of being enough to generate required BRP with aqueous medium.It can make Make to contain CO with any suitable scheme₂Gas contacted with aqueous medium.For example, target contact scheme includes but unlimited In：It is in direct contact scheme, such as the aqueous medium bubbled gas across certain volume；Current contacting scheme, i.e., in one-way flow Gaseous stream and liquid phase stream between contact；Counter-current configuration, i.e., it is indirectly in the gaseous stream of reverse flow and liquid phase stream It touches.Contact can by using such as can be suitable injector, bubbler, fluid venturi reactor, sprinkler, gas filtration Device, sprayer, column plate or filling tower reactor etc. are reached.

Contact to contain CO₂Gas present in major part CO₂Into in solution to generate the item of bicarbonate ion Occur under part.Mostly, refer to 10% or more, such as 50% or more, including 80% or more.In some cases Under, 5% or more of all bicarbonate ions in the liquid solution (mother liquor) of initial bubble, such as 10% or more, including 20% or more becomes to be isolated in LCP.

The variable temperatures of the aqueous medium contacted with gas.In some cases, temperature is at -1.4 to 100 DEG C, and such as 20 To 80 DEG C, and include in the range of 40 to 70 DEG C.In some cases, temperature can in -1.4 to 50 DEG C or higher, such as -1.1 To 45 DEG C or higher.In some cases, using cooling water temperature, wherein the temperature can at -1.4 to 4 DEG C, In the range of -1.1 to 0 DEG C.Although initial aqueous medium can be cooled down to obtain required temperature, in some cases, can adopt With the natural aqueous medium with required Optimal Temperature.For example, when aqueous medium is ocean or seawater, ocean Or seawater can have the place residing for required temperature to obtain from water.In some cases, the water is obtained to may include from water surface A certain depth below (such as ocean surface) obtains water, wherein in some cases, the depth can at 10 to 2000 meters, such as 20 To 200m.

In some cases, using compared with warm temperatures.For example, in some cases, the temperature of aqueous medium can be 25 DEG C or higher, such as 30 DEG C or higher, and in some embodiments, it can be at 25 to 50 DEG C, in the range of 30 to 40 DEG C. Although in said case, given aqueous medium can be warmed to reach these temperature, in some cases, aqueous medium can It is obtained from the naturally occurring source under required warm temperatures, or from the man-made origin for providing required temperature, such as from work The acquisitions such as the output end of industry (such as electric power) factory cooling system.

Containing CO₂Gas and aqueous medium be suitable for generate needed for rich in bicarbonate radical product pressure under contact. In some cases, the pressure of contact conditions is selected to provide optimal CO₂Absorb, wherein the pressure can 1atm extremely 100atm, in the range of 1atm to 10atm.When contacting when naturally occurring at the place under 1atm, can be used any Suitable scheme makes the pressure increase to required pressure.In some cases, contact is happened at there are at optimum pressure, such as is being located At water body (such as ocean or sea) surface place below.In some cases, contain CO₂Gas and buffered with bicarbonate water Property medium contact be happened at a certain depth below water surface (such as ocean surface), wherein in some cases, the depth Degree can be at 10 to 1000 meters, in the range of 10 to 100 meters.Expediently, in said case, bicarbonate radical is rich in for generating The water of product (and LCP in some cases) can be obtained under depth identical with residing depth is combined.It is connecing After touching, as needed, product (may include LCP) can be elevated go back to surface for further processing.Alternatively, product can be released Residing environment is generated to it, such as in deep water, in the environment, its sustainable prolonging period keeps stablizing.Work as product When being released into environment, it can be made further deeply to decline, such as drop to ocean bottom.

LCP accelerating agents

In some cases, contain CO₂Gas and aqueous medium be to be contacted in the presence of LCP accelerating agents.LCP accelerating agent packets It includes by making the formation of the LCP in BRP compositions stabilize the entity to work.Target LCP accelerating agents include LCP promotion property Cation, the cation can exist together with suitable pair anion.The example of LCP promotion property cations includes but not limited to two Valence alkaline earth metal cation, such as Ca²⁺、Mg²⁺And combinations thereof.It can be used as other targets two of LCP accelerating agents alone or in combination Valence cation includes but not limited to：Be²⁺、Ba²⁺、Sr²⁺、Pb²⁺、Fe²⁺、Hg²⁺Deng.Can be or can not be divalent other targets sun Ion includes but not limited to：Na⁺,K⁺,NH₄ ⁺And Li⁺And Mn, Ni, Cu, Zn, Ce, La, Al, Y, Nd, Zr, Gd, Dy, Ti, Th, U, the cationic substance of La, Sm, Pr, Co, Cr, Te, Bi, Ge, Ta, As, Nb, W, Mo, V etc..

The pair anion of LCP accelerating agents can be any suitable anions.Desired anion includes but not limited to：Cl^-、 SO₄ ^2-、NO₃ ^-、BO₄ ^-, silicate, phosphate radical etc..

The amount of the LCP accelerating agents of offer can be changed as needed.In some cases, with water phase and CO₂Source After combination, the amounts of existing LCP accelerating agents is in 1 to 80%, such as 5 to 10%, and in the range of including 6.9 to 8.6 dry weight %.

In some cases, it has included the water phase for being suitble to LCP accelerating agents to be for the water phase in method.For example, it wraps Divalent or other cationic source are included, and therefore can be used for the naturally occurring water in the embodiment of theme BRP generation systems Property medium includes but not limited to：It is such as above-mentioned from the aqueous medium of the acquisitions such as sea, ocean, river mouth, lagoon, brine, alkali lake, inland sea Aqueous medium.

Catalyst

When needed, make to contain CO₂Gas and buffered with bicarbonate aqueous medium mediate CO₂It is converted to bicarbonate radical Catalyst (i.e. absorbing catalyst) in the presence of contact.Target absorption catalyst is under the pH levels being in the range of 8 to 10, Make from the CO dissolved₂Generate the increased catalyst of rate of bicarbonate ion.Rate increase (such as compared to there is no catalysis The control of agent) magnitude it is alterable, and in some cases, compared to suitable control, magnitude be it is 2 times or more large, such as 5 times or Bigger, such as 10 times or bigger.In some cases, catalyst is carbon dioxide specific catalyst.Target carbon dioxide is special The example of anisotropic catalyst includes enzyme, such as carbonic anhydrase；Synthetic catalyst, such as Koziol, " Toward a Small Molecule,Biomimetic Carbonic Anhydrase Model:Theoretical and Experimental Investigations of a Panel of Zinc(II)Aza-Macrocyclic Catalysts,”Inorganic Chemistry(2012)51:Transition-metal catalyst those of described in 6803-6812；Colloidal metal particles, such as Bhaduri And Siller, " Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage,”Catalysis Science& Technology(2013)DOI:Those of described in 10.1039/c3cy20791a etc., such as colloidal metal oxide particle.

Target carbonic anhydrase includes naturally occurring (i.e. wild type) both carbonic anhydrase and its mutant.Specific mesh Marking carbonic anhydrase includes but not limited to：α-CA comprising mammal carbonic anhydrase, such as cytoplasm CA (CA-I, CA-II, CA- III, CA-VII and CA XIII) (CA1, CA2, CA3, CA7, CA13), mitochondria CA (CA-VA and CA-VB) (CA5A, CA5B), Secretion CA (CA-VI) (CA6) and the relevant CA of film (CA-IV, CA-IX, CA-XII, CA-XIV and CA-XV) (CA4, CA9, CA12,CA14)；β-CA comprising prokaryotes and plant chloroplast CA；γ-CA such as see methane generation property bacterium In；Deng.Target carbonic anhydrase further includes U.S. Patent number 7, those of described in 132,090, the disclosure with The mode of reference is incorporated herein.Target carbonic anhydrase includes that specific activity is 10³s^-1Or higher, such as 10⁴s^-1Or higher, including 10⁵s^-1Or those of higher.When employed, catalyst is effectively to provide the required rate that bicarbonate radical for example as described above generates Increased amount exists.In the case where catalyst is some cases of enzyme, the activity of enzyme in an aqueous medium can be 10³To 10⁶s^-1, such as 10³ To 10⁴s^-1, and include 10⁵To 10⁶s^-1In the range of.When employed, can be used any proper method make catalyst (such as Enzyme, such as carbonic anhydrase) can be used in reaction, as connected by catalyst or in addition association that catalyst is stablized solid carrier (such as permeable membrane)；Stablize porous media of association etc. by catalyst and its；Catalyst, which is fixed on, wherein (to be connected thereto) Large surface；Or with the catalyst in solution state, such as it can recycle after usage.The reality of adoptable catalyst mode Example is including but not limited to those of described in U.S. Patent number 7,132,090；The disclosure is by reference It is incorporated herein.

Target synthetic catalyst include be synthetically prepared contain transition metal complex, be produced for example as described above at The bionic model of carbonic anhydrase.Specific synthetic catalyst includes but not limited to：Transition metal nitrogen heterocyclic ring catalyst, such as have There are zinc (II) nitrogen heterocyclic ring catalyst of the big ring in 9,12,13 or 14, such as Koziol, " Toward a Small Molecule, Biomimetic Carbonic Anhydrase Model:Theoretical and Experimental Investigations of a Panel of zinc(II)Aza-Macrocyclic Catalysts,”Inorganic Chemistry(2012)51:Described in 6803-6812；Metallic catalyst based on imidazoles and indoles, such as U.S. Published Application Institute in number US20110293496, U.S. Published Application No US20120199535 and U.S. Published Application No US20110151537 Zinc (II) catalyst stated；Based on the catalyst of aminopyridine base, such as such as Feng, " A Highly Reactive Mononuclear Zn(II)Complex for Phosphodiester Cleavage,”Journal of the American Chemical Society(2005)127:Described in 13470-13471；Based on pyrazolyl boron hydrogen radical and pyridyl group The compound of butylthiomethyl, such as such as Sattler and Parkin, " Structural characterization of zinc bicarbonate compounds relevant to the mechanism of action of carbonic anhydrase,"Chemical Science(2012)3:Described in 2105-2109.Target synthetic catalyst includes specific activity 10²s^-1Or higher, such as 10³s^-1Or higher, including 10⁴s^-1Or those of higher.When employed, synthetic catalyst is effectively to carry For for example as above existing for the increased amount of required rate that the bicarbonate radical described in carbonic anhydrase generates.When employed, can make With the synthesis for for example as above making such as nitrogen heterocyclic ring transition-metal catalyst for any proper method described in carbonic anhydrase Catalyst can be used in reaction.

Metal target nano-particle includes colloidal transition metal particle that is commercially available and being synthetically prepared.Specific glue Body metallic includes but not limited to：Metal nanoparticle, such as Bhaduri and Siller, " Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage,”Catalysis Science&Technology(2013)DOI:10.1039/c3cy20791a Described in nickel nano particle (NiNP).Target colloidal metal particles include that specific activity is 10²s^-1Or higher, such as 10³s^-1Or more Height, including 10⁴s^-1Or those of higher.When employed, colloidal metal particles are effectively to provide for example as above for carbonic anhydride The increased amount of required rate that bicarbonate radical described in enzyme generates exists.When employed, it can be used for example as above for carbonic anhydride Any proper method described in enzyme makes the colloidal metal particles of such as transition metal nanoparticles can be used in reaction.It is suitable for Catalyst with metal nanoparticles in the embodiment described herein is further described in the U.S. submitted on March 15th, 2013 and faces When patent application serial numbers 61/793,585 in；The disclosure of the application is hereby incorporated herein by.

In one embodiment, the unsegregated bicarbonate radical of definite part can be consumed to regeneration carbonate in LCP To start again at absorption process.For example, aqueous medium may include alkali metal cation, such as sodium cation.When there are sodium sun When ion, aqueous medium can be sodium carbonate liquor.In said case, for each CO of absorption₂, there are a carbonates to generate Two bicarbonate radicals.One in two bicarbonate radicals is used to then go out as cohesion liquid phase separation, and another is used to pass through CO is formed under carbonic anhydrase, synthetic catalyst or colloidal metal particles₂Sodium carbonate is regenerated with sodium carbonate.

In some cases, including the amine of primary amine, secondary amine and tertiary amine can be used as CO₂The reinforcing agent and/or bicarbonate of dissolving Catalyst during radical ion is formed provides.Target primary amine includes but not limited to：Ammonia, 2- amino -2- methylols-propane -1,3- Glycol (TRIS), 2-amino-2-methyl-1-propanol (AMP), melamine, amino -2- propyl alcohol, arginine, gathers at monoethanolamine (MEA) Arginine etc..Target secondary amine includes but not limited to：It is diethanol amine (DEA), morpholine, 2- (tert-butylamino) ethyl alcohol (TBAE), double (2- hydroxypropyls) amine, piperazine, amino ethyl ethanolamine, N- [three (methylol) methyl] -3- amino propane sulfonic acids (TAPS) etc..Mesh Marking tertiary amine includes but not limited to：2,2 ', 2 ", 2 " '-(ethylene nitrilo-) tetraethoxide (THEED), methyl diethanolamine (MDEA), poly- melamine-formaldahyde (Tysol SM), triethanolamine (TEOA), triethanolamine acetate, three (2- hydroxypropyls) amine etc.. When it is present, the amount of these amine is alterable, and in some cases, 1% to 80%, such as 10.2% to 21.7 dry weight % In range.

LCP stabilization systems

In some cases, contain CO₂Gas and aqueous medium can be contacted in the presence of LCP stabilization systems, it is described steady Surely changing system can be grouped as by one or more groups.When LCP compositions are such as two-phase systems as described above, it can by regarding For microemulsion, such as by the dynamics or Thermodynamically stable of two kinds of immiscible liquids that interface is amphipathic or amphiphile, amphiphilic molecule is stablized Dispersion liquid.In the embodiment described in which, any suitable microemulsion stabilization system can be used.Goal systems includes but not limited to real Those of the volume stability of emulsion droplets in existing microemulsion and/or surface area (S.A) stabilization removal.Lotion surface nature and Bulk solution property can be operated to inhibit or promote totality BRLCP formation and/or stability as needed.

In some cases, stabilization system is the system for promoting lotion volume stability.When the driving force that LCP is formed is When the association of the high chaotropic sequence water of hydration, adds and can be used in high chaotropic sequence (i.e. water-bound is destructive) additive to solution Facilitate smaller, more numerous droplets, because of S.A.:Volume ratio will reduce in the state of the equilibrium, and therefore lead to more LCP It is formed.It distributes in supreme chaotropic sequence phase, and some associated additives that can be used as phase volume stabilizer include but not limited to： Cl^-、Br^-、I^-、K⁺, ammonia, ammonium, nitrate anion, nitrite anions, the molecule with the functional group based on nitrogen and polymer and minimum dredge Aqueous substance.Also it is concerned with low chaotropic sequence (water-bound formative) solute additive, wherein the example packet of the additive It includes but is not limited to：Mg²⁺And Li³⁺.When it is present, the amount of the additive is alterable, and in some cases, 1% to In the range of 80%, including 5.2% to 24.4 dry weight %.

In some cases, stabilization system is to promote lotion surface area (S.A.) stabilized system.In high chaotropic sequence The amphiphilic substance that row are mutually aligned with the interface between low chaotropic sequence phase can influence the Size Distribution and total amount of LCP phases.In the presence of Strong amphiphilic substance (such as surfactant) can be used for making S.A. stabilization removals minimum, and generate smaller, more numerous small Drop.When it is present, the amount of the additive is alterable, and in some cases, dry 1 to 80%, including 2.6 to 6.9 In the range of weight %.

The stabilizer includes but not limited to：Amino acid (such as glutamic acid, aspartic acid, arginine, lysine and group ammonia Acid), polycarboxylic acids, Si, melamine sulfonates polycondensation product etc. and electrically charged polymeric material, including polyelectrolyte is (such as poly- Anion and polycation), polypeptide and class peptide.

Target polyelectrolyte can greatly change, and in some cases, have 900 dalton (dalton) or bigger, Such as 1,000 dalton or bigger, including 1,500 dalton or bigger, in some cases in 900 to 500,000 dalton, such as Molecular weight in the range of 1,000 to 50,000 dalton.Target polyelectrolyte may include organic and/or inorganic component, and It may include single under the conditions of certain pH or dual electrically charged monomer residue, the pH lower bands being such as in the range of 6 to 8 (anion) unit of negative electrical charge.Anionic functional base includes but not limited to：Phosphate radical, phosphonate radical, sulfate radical, sulfonate radical, carboxylic Acid group, polyphosphoric acid root and polycarboxylate.Various anionic monomer residues may include phosphate, acrylates, maleate, Methacrylate, vinyl carboxymethyl ester etc..Monomer can by homopolymerization or copolymerization, wherein when needed organic monomer with extensively it is more Kind hydrocarbon or miscellaneous substituted fluoride monomers.Neutral monomer may be from two to six, such as two to four carbon atom, have one A to three, such as one to two can be oxygen (such as oxygroup and oxo base, the carbonyl oxo base and non-oxo base-carbonyl of carboxyl Deng) hetero atom.Illustrative neutral monomer suitable for combined polymerization includes methyl acrylate, methyl vinyl ether, acrylic acid hydroxyl second Ester, ethylene, vinyl acetate etc..The inorganic polyelectrolyte of target includes but not limited to：Quadrafos such as has nine or more Phosphate group, such as ten two or more phosphate groups, and the poly- phosphorus of 100 or less phosphate group in some cases Hydrochlorate, such as Quadrafos with 20 to 30 phosphate groups.

The reagent further includes peptide reagent, such as peptide, peptide and protein and peptide mimics, such as class peptide, beta-peptide etc..Mesh The variable mass of peptide reagent is marked, in some cases, in 125 to 500,000 dalton, such as 1,000 to 100,000 dongle , and in the range of including 10,000 to 50,000 dalton.The example of target polypeptides includes but not limited to：Poly- asparagus fern ammonia Acid, polyglutamic acid, polylysine, poly-asparagine or polyhistidyl and electrically charged and uncharged amino acid residue it is miscellaneous Polymers.Amino acid residue can be L or D amino acid, and can be naturally occurring or non-naturally occurring.The reagent further includes more Sugared reagent, such as starch, pectin, cellulose, chitin and acidic polysaccharose.The variable mass of desired polysaccharide reagent, in some feelings In 125 to 500,000 dalton, such as 1,000 to 100,000 dalton, and include 10,000 to 50,000 dalton under condition In the range of.

Silica source

When needed, make to contain CO₂Gas and aqueous medium in silica source, (and optionally silica specificity is urged Agent) in the presence of contact.Silica source can be pure silicon dioxide or other chemical combination including silica Yu such as minerals The composition of object combination, as long as silica source is enough for example to compensate come in CO by self-catalysis silica₂It is assigned during hydration Give required basicity.In some cases, silica source is naturally occurring silica source.Naturally occurring titanium dioxide Silicon source includes can be in sand or the rock containing silica of larger rock formation.When source is larger rock, in some cases, Rock has been decomposed to reduce their size, and increases their surface area.It is contemplated that being existed by longest dimension 0.01mm to 1 meters, as the group in the range of 0.1mm to 500cm, including 1mm to 100cm, such as 1mm to 50cm be grouped as two Silica source.When needed, silica source can be surface-treated to increase the surface area in source.

A variety of naturally occurring silica sources of difference can be used.The naturally occurring silica source of target includes but unlimited In igneous rock, the rock includes：Ultramafites, such as komatiite (Komatiite), picrite basalt (Picrite Basalt), kimberlite (Kimberlite), Potassic lamprophyres (Lamproite), peridotite (Peridotite)；Magnesium iron Matter rock, such as basalt (Basalt), diabase (Diabase) (trachybasalt (Dolerite)) and gabbro (Gabbro)；It is neutral Rock, such as andesite (Andesite) and diabase (Diorite)；Neutral aplite (intermediate felsic rock), Such as dacite (Dacite) and granodiorite (Granodiorite)；And aplite, such as rhyolite (Rhyolite), fine grain Rock-pegmatite (Aplite-Pegmatite) and granite (Granite).

Also it is concerned with synthetic silica source.Synthetic silica source includes but not limited to waste stream, such as：Mining is useless Object；Fossil fuel calcination lime-ash；Slag, such as Iron-ore Slag, phosphorus ore slag；Cement kiln refuse；Olein refinery/petrochemical refinery Waste, such as oil field and methane layer salt solution；Coal seam refuse, such as gas generate brine and coal seam salt solution；Paper process waste；Water Softening, such as ion exchange waste brine；Silicon handles waste；Agricultural wastes；Medal polish waste；High pH fabrics waste；And alkali Slag.Mining wastes include from extracting metal or any waste that is another valuable or being applicable in minerals from soil.Target waste packet The waste from the mining for increasing pH is included, including：Red soil from Bayer aluminium extraction processes；From to seawater progress magnesium The waste of extraction, such as at Moss Landing, Calif.；And the waste from the other mining technologies for being related to leaching. The lime-ash of technique (such as coal-fired power plant) from calcination fossil fuel generates often rich silica containing lime-ash.In some implementations In scheme, the lime-ash generated by calcination fossil fuel (such as coal-fired power plant) is provided as silica source, including flying dust slag (such as exiting the lime-ash of chimney) and bottom ashe.

Containing CO₂Gas and buffered with bicarbonate aqueous medium contact during existing silica source amount it is variable Change, as long as it is enough for example to compensate come in CO by self-catalysis silica₂Basicity needed for being provided during hydration.It uses Amount by depending on the property of the aqueous medium of the volume in particular silica source and reactor, buffered with bicarbonate, contain CO₂ Gas property etc..When make contain CO₂Gas and the aqueous medium of buffered with bicarbonate when contacting in the reactor, at some In the case of, the percent by volume of the reactor occupied by silica source can 1 to 99%, such as 5 to 95%, and include 10 to In the range of 90%.In some cases, the strong acid dissolution silica source such as HCl is not had to.

When needed, it is possible to provide enhance the silica specific catalyst of the rate of dissolution of silica source.Rate increases Add the magnitude of (such as compared to there is no the controls of catalyst) alterable, and in some cases, compared to suitable control, Magnitude is 2 times or more, such as 5 times or more, such as 10 times or more.Final catalyst includes that specific activity is 10²s^-1Or higher, Such as 10³s^-1Or higher, including 10⁴s^-1Or those of higher.Final catalyst includes both enzyme catalyst and non-enzymatic catalysis agent, such as U.S. Patent number 7,229, silicatein those of described in 807, such as, but not limited to Zhou etc., " Efficient Catalysis of Polysiloxane Synthesis by SilicateinαRequires Specific Hydroxy and Imidazole Functionalities,”Angewante Chemie International Edition(1999) 38:779-782 and Roth etc., " Bifunctional Small Molecules Are Biomimetic Catalysts for Silica Synthesis at Neutral pH,”Journal of the American Chemical Society (2005)127:Those of described in 325-330.Target enzyme catalyst includes but not limited to：Silicatein, silica enzyme Deng.Target non-enzymatic catalysis agent includes but not limited to：Macrocyclic polyamine etc..

About silica source and their purposes other detaile descriptions on March 15th, 2013 U.S. submitted it is interim In patent application serial numbers 61/793,731, the disclosure of the application is hereby incorporated herein by.

Product rich in bicarbonate radical

Above method causes to generate the product (BRP) rich in bicarbonate radical.As summarized on, BRP compositions are that feature exists In the higher composition of the concentration of bicarbonate ion, wherein in some cases, the concentration of bicarbonate ion can be 5, 000ppm or higher, such as 10,000ppm or higher, including may achieve 15,000ppm or higher.In some cases, bicarbonate Radical ion can in 5,000 to 20,000ppm, such as 7,500 to 15,000ppm, including 8, in the range of 000 to 12,000ppm.? Under some cases, the total amount of the bicarbonate ion in BRLCP can be in 0.1wt.% to 30wt.%, and such as 3 to 20wt.%, including In the range of 10 to 15wt.%.In some cases, BRP includes the bulk liquid of the droplet of phase containing liquid condensation (LCP), example Such as bulk solution, as summarized on.After preparing BRP compositions, BRP compositions can be stored as needed or further Operation.

BRP is stored

In some embodiments, the sustainable prolonging period of BRP compositions is stored (even if not indefinitely), thus Isolation is used to generate the initial CO of BRP compositions certainly₂The CO that source obtains₂.For example, in cold climates, BRP groups can be made It closes object and is frozen up to weather condition permission product defrosting, further operating (such as described below) can be carried out to product at this time.Production Object BRP compositions can be stored in geologic reservoir until be required, or the composition is even made to be mixed with geology saline solution, And it is made to mineralize on the spot.Therefore, after generating BRP compositions, further operating (if it is fundamentally occurring) can It is delayed by one period, such as 1 day or longer, 1 week or longer, 1 month or longer, 3 months or longer, 6 months or longer, 1 year Or it is longer etc..In the case where needing to store BRP compositions or its component (such as LCP), product can be stored in sealing container, Such as in bucket or larger container, and the atmosphere including preventing exhaust, such as pure CO may or may not be stored in₂Atmosphere etc. In environment.

Include in BRP the droplet of LCP some cases under, BRP product compositions can be made to be subjected to separation scheme, such as wherein The LCP of product rich in bicarbonate radical is set to be detached with bulk solution, such as so that further operating is (such as storing, generating carbon Hydrochlorate minerals etc.).Any suitable separation scheme can be used, wherein target protocol includes but not limited to：Cyclone hydraulic separators, sedimentation Formula centrifuge, ultracentrifugation, Epurimat, sled bed clarifier etc..

In certain embodiments, it is desirable to form bicarbonate solid for multiple use, such as generate Sodium bicarbonate (sodium bicarbonate).

BRP additives/admixture

When needed, BRP product compositions as prepared or can add other components (such as chemical admixture group Point) be used in various applications afterwards.For example, BRP compositions can as needed as produced or with other groups of subassemblys It is used as cement additive (such as coagulating fluid or together with another coagulating liq) afterwards.

In some cases, product BRP compositions are used as the bicarbonate additive of cement.Term as used herein " bicarbonate additive " refer to include bicarbonate radical (HCO₃ ^-) ion or its solid derivative (such as such as institute more fully below State) be liquid or solid any composition.When bicarbonate additive is liquid composition, the liquid composition It can be used as unique coagulating liq component when generating condensable cement composition or it can be together with one or more for example as following Other coagulating liqs described in more detail are used together.The pH of liquid carbonic acid hydrogen salt additive is alterable, and certain In the case of, 4 to 12, as in the range of 5 to 9, such as 6 to 8.The amount of bicarbonate ion in bicarbonate additive can root It is changed according to needs.For liquid composition, in some cases, the total amount of bicarbonate radical can 0.1wt.% extremely 30wt.%, as in the range of 3 to 20wt.%, including 10 to 15wt.%.

As mentioned above, the bicarbonate additive for generating given condensable cement composition can be liquid or consolidate Body.In the presence of in solid form, the solid is the dehydrated form of liquid carbonic acid hydrogen salt additive.Solid can be that use is used for Consolidate from any suitable scheme of liquid removal water, such as evaporation, freeze-drying etc. from what liquid carbonic acid hydrogen salt additive generated Body.After being combined with the water of suitable volume, obtained solid is dissolved in the water to generate liquid carbonic acid hydrogen salt for example as described above Additive.In some cases, recovery is by combination drying bicarbonate additive and enough liquid (such as aqueous Jie Matter, such as water) reach, wherein the ratio of the liquid and solid that use is alterable, and in some cases, 1,000,000 To 1, in the range of 100,000 to 10.Solid carbonic acid hydrogen salt additive may include a variety of different grain sizes and size distribution.Citing For, in some embodiments, solid carbonic acid hydrogen salt additive may include size at 1 to 10,000 μm, such as 10 to 1,000 μ M, and include the particle in the range of 50 to 500 μm.

Other details about BRP bicarbonate additives are provided in the U.S. Provisional Application sequence submitted on April 1st, 2013 In the U.S.Provisional Serial 61/819,427 that row number is submitted on May 3rd, 61/807,230 and 2013, the public affairs of the application Content is opened to be hereby incorporated herein by.

In some cases, BRP compositions can be made to be combined to produce BRP blending with one or more other chemical admixtures Object.In the blend composition, the variable of BRP components.In some cases, BRP components be with 0.1 to 25, as the amount in the range of 1 to 15, including 5 to 10wt% exists.In some cases, admixture contains a certain amount of presence CO in solution₂, such as in forms such as bicarbonate radical, BRP, the amount is more than the basicity based on solution, will be predicted molten Amount in liquid, wherein in some cases, factor that actual amount is more than premeasuring is 1.1 or bigger, such as 1.25 or bigger, including 1.5 or bigger, such as two or more, 5 or bigger, 10 or bigger, including 25 or bigger.

Chemical compound ingredients be by it is one or more be added in cement with to cement assign desirable feature or Property, such as to improve the property of cement the chemical substance that it was readily available or was more suitable for specific purpose is formed.When When concrete is used together, chemical admixture is certain not to give it in being added in concrete for powder or fluid form The substance of the feature of normal concrete mixture acquisition can be used.The chemistry being included in given cement/concrete mix blends The amount of object visually the property of chemical blend composition and change.In certain embodiments, it is included in cement/concrete mixing The amount of chemical blend composition in object can be in the range of 1% to about 50% (w/w), wherein in some cases, amount is 25% or less, such as 20% or less, such as 15% or less, including 10% or less, such as 5% or less, such as 2.5% or Less.

Target chemical admixture includes but not limited to：Plasticiser (such as may be added to that and carried in condensable cement composition For it with improved machinability in order to reinforcement effect power reduction under pour and can add for uniform flow without The compound strengthened in condensable cement composition needed for space is left a void under reinforcing bar)；Accelerator, retarding agent, air folder Band agent, foaming agent, water-reducing agent, corrosion inhibitor and pigment or colorant.

Accelerator is used to increase the solidification rate (being hydrated) of condensable cement composition, and is needing condensable cement There is particular importance in the application of composition quick-hardening and in cryogenic applications.Retarding agent is used to slow down hydration rate, And increase can be used for pouring into condensable cement composition and be formed as the time of required shape.Retarding agent is in condensable There is particular importance in the application that cement composition uses under hot climate.Air entrainment agent is for making micro-bubble be distributed In entire condensable cement composition.Air entrainment agent has special for being utilized in the region for being subjected to cold snap Value, because the bubble of small entrainment helps to reach certain contraction and expand to protect condensable cement composition from cold Freeze-thawization is damaged.Pigment and colorant can be also added in concrete for beautiful purpose to provide it with required color spy Sign.Therefore, target admixture includes but not limited to：Setting accelerator, condensation retarding agent, air entrainment agent, antifoaming agent, alkali reaction Property depressant, bonding admixture, dispersant, coloring admixture, corrosion inhibitor, moisture-proof admixture, gas forming agent, permeable Property depressant, pumping auxiliary agent, shrinkage-compensating admixture, antifungal admixture, sterilization admixture, insecticidal admixture, rheology Conditioning agent, wetting agent, intensity reinforcing agent, waterproofing agent etc..

Setting accelerator is used to accelerate condensation and the early strength progress of condensable cement composition.It can be used as admixture Setting accelerator can be but be not limited to the nitrate of alkali metal, alkaline-earth metal or aluminium；The nitrous acid of alkali metal, alkaline-earth metal or aluminium Salt；The rhodanate of alkali metal, alkaline-earth metal or aluminium；Alkanolamine；The thiosulfate of alkali metal, alkaline-earth metal or aluminium；Alkali gold Belong to, the hydroxide of alkaline-earth metal or aluminium；The carboxylate (such as calcium formate) of alkali metal, alkaline-earth metal or aluminium；Poly- hydroxy alkyl Amine；The halide salts (such as chloride) of alkali or alkaline earth metal.

Condensation retardance admixture can also be used.Condensation retardance (also referred to as delay condensation or hydration control) admixture is for hindering Rate of setting that is stagnant, postponing or slow down condensable cement composition.They can start after initial ingredients or in hydro-combination process Being sometime added in condensable cement composition later.Condensation retarding agent is for offsetting hot weather to condensable cement The acceleration of the condensation of composition, or when for example there is condition difficulty is poured, when something goes wrong to building site delivering, delay can coagulate The initial condensation of cement composition is tied, or having time is allowed to carry out special polishing process.Most of condensation retarding agents also function as low Grade water-reducing agent, and can also be used for carrying certain air into condensable cement composition secretly.Workable retarding agent include but It is not limited to oxygroup-boron compound, corn syrup, lignin, polyphosphonic acid, carboxylic acid, hydroxycarboxylic acid, polycarboxylic acids, hydroxy carboxylic acid (such as Fumaric acid, itaconic acid, malonic acid, borax, gluconic acid and tartaric acid), it is lignosulfonates, ascorbic acid, different anti-bad Hematic acid, sulfonic-acrylic copolymer and their corresponding salt, poly- silicol, polyacrylamide, carbohydrate and its mixing Object.

Also it is concerned with air entrainment agent as admixture.Term air entrainment agent includes that will carry air secretly in cement composition Any substance in object.Some air entrainment agents can also reduce the surface tension of composition at low concentrations.Air entrainment blends Object is used for intentionally will be in micro- entraining air bubbles to condensable cement composition.Air entrainment, which can significantly improve, to be freezed and is thawing The durability of the condensable cement composition of moisture is exposed to during cycle.In addition, the air of entrainment can be greatly improved to by changing Learn the resistance that surface is peeled off caused by deicer.Air carries the machinability for also increasing fresh condensable cement composition secretly, together When eliminate or reduce separation and be lost in.Wood resin, natural resin, synthesis are can be selected from for reaching these required substances acted on Resin, lignosulfonate, petroleum acids, protein material, aliphatic acid, resin acid, alkylbenzene sulfonate, sulfonated hydrocarbon, rosin Quillaia saponaria Fat, cationic surfactant, nonionic surfactant, natural rosin, synthesizes rosin, is inorganic anion surfactant Air entrainment agent, synthetic detergent and their corresponding salt and its mixture.Air entrainment agent is to be produced in cement composition The amount addition of air level needed for raw.

Also it is concerned with antifoaming agent as admixture.Antifoaming agent is for reducing the air content in cement composition.It can use The example of antifoaming agent in cement composition includes but not limited to mineral oil, vegetable oil, aliphatic acid, aliphatic ester, hydroxyl official It can compound, amide, phosphate, metallic soap, silicone, the polymer containing propylene oxide part, hydrocarbon, alkoxylate hydrocarbon, alcoxyl Base polyoxyalkylene, tributyl phosphate, dibutyl phthalate, octanol, the water-insoluble ester of carbonic acid and boric acid, acetylenic glycols, Ethylene oxide-propylene oxide block copolymer and silicone.

Also it is concerned with corrosion inhibitor as admixture.Corrosion inhibitor in condensable cement composition is for protecting The reinforcing material (such as steel of embedding) of embedding is from corrosion.The high alkaline nature of most of condensable cement compositions causes As steel material on form passivity and non-aggressive protective oxide film.Deicer or sea are come from however, carbonating or existing The chlorion of water can destroy or permeate the film, and cause to corrode.Corrosion-inhibiting admixture chemically checks this Corrosion reaction.It is most commonly used for inhibiting the substance of corrosion being calcium nitrite, sodium nitrite, sodium benzoate, certain phosphate or fluorine Silicate, fluorine aluminite, amine and related chemical species.

Also it is concerned with moisture-proof admixture.Moisture-proof admixture, which reduces, has low cement, high water cement ratio rate or aggregation The permeability of the condensable cement composition of defect.These admixtures retardance moisture infiltrates into condensation cement composition, and And include certain soap agents, stearate and oil product.

Also it is concerned with gas and forms admixture.Gas forming agent or gas are formed reagent and are sometimes added to indivisible To cause slightly to expand before the hardening in condensable cement composition.Swell increment depend on gases used forming material amount and The temperature of fresh mixture.Aluminium powder, resin soap and natural plant gum or animal glue, saponin or hydrolysis protein can be used as gas and formed Agent.

Also it is concerned with permeability depressant.Permeability depressant is for reducing water under pressure through cement composition Object is transmitted residing rate.Silica fumes, flying dust slag, the slag of grinding, natural volcanic ash, water-reducing agent and latex can For reducing the permeability of cement composition.

Also it is concerned with rheology modifier admixture.Rheology modifier can be used for increasing the viscosity of cement composition. The suitable example of rheology modifier includes aerosolization silica, colloidal silicon dioxide, hydroxyethyl cellulose, hydroxy propyl cellulose Or mixtures thereof element, flying dust slag, mineral oil, HECTABRITE DP, polyoxyalkylene, polysaccharide, natural jelly.

Can bacterium and fungi be partially controlled on the concrete of hardening by using antifungal and sterilization admixture Growth among or.The example of these substances include more halogenation phenol, Trane (dialdrin) lotion and copper compound.

Any suitable scheme can be used to prepare BRP admixtures.For example, chemical admixture can be made to be combined with BRP with Generate BRP admixtures.In terms of the dry weight of two kinds of components, the ratio of BRP and chemical admixture are alterable, and in some cases Under, 1 to 10, in the range of 1 to 1.Any suitable scheme can be used to combine these components, such as wherein add under mixing Add a certain amount of BRP components into chemical admixture, or and vice versa.

Such as depending on the special properties of accelerating agent used, existing other chemical compound ingredients etc., such as institute as above The BRP admixtures stated may act as a variety of different types of admixtures.Therefore, admixture may act as that admixture, diminishing is accelerated to blend Object, diminishing and condensation retardance admixture, high scope diminishing admixture and middle range diminishing admixture, are respectively subject to herein It is described in further detail.

Accelerate admixture commonly used in increasing the solidification rate (be hydrated) of condensable cement composition, and need can Cement composition quick-hardening is condensed, and with particular importance in the application with early strength progress.Accelerate admixture It may include：The nitrate of alkali metal, alkaline-earth metal or aluminium；The rhodanate of alkali metal, alkaline-earth metal or aluminium；Alkanolamine；Alkali gold Belong to, the thiosulfate of alkaline-earth metal or aluminium；The hydroxide of alkali metal, alkaline-earth metal or aluminium；Alkali metal, alkaline-earth metal or aluminium Carboxylate (such as calcium formate)；Poly- hydroxy alkyl amine；The halide salts (such as chloride) of alkali or alkaline earth metal.Including The specific example of Common materials in accelerating admixture includes：Calcium chloride, triethanolamine, sodium sulfocyanate, sodium formate/formic acid Calcium, sodium nitrite/calcium nitrite, calcium nitrate, aluminate and silicate.

Diminishing admixture is commonly used in making the water content of cement composition to reduce by 5% or more.Diminishing admixture may include： Lignosulfonic acid and their salt, hydroxy carboxylic acid their salt, polysaccharide, melamine polycondensation product, naphthalene polycondensation product and poly- carboxylic Hydrochlorate.

Diminishing and condensation retardance admixture are commonly used in making the water content of cement composition to reduce by 5% or more, and prolong The setting time of slow cement composition.Diminishing and condensation retardance admixture may include：Salt, the hydroxylating carboxylic of lignosulfonic acid and they Acid and their salt, polysaccharide, melamine polycondensation product, naphthalene polycondensation product, polycarboxylate, oxygroup-boron compound, primverose Slurry, lignin, polyphosphonic acid, carboxylic acid, hydroxycarboxylic acid, polycarboxylic acids, hydroxy carboxylic acid (such as fumaric acid, itaconic acid, malonic acid, Borax, gluconic acid and tartaric acid), lignosulfonates, ascorbic acid, arabo-ascorbic acid, sulfonic-acrylic copolymer and it Corresponding salt, poly- silicol, polyacrylamide, carbohydrate and its mixture.

High scope diminishing admixture is commonly used in making the water content of cement composition to reduce 12-40% or more, and increase is collapsed It collapses, reduction pours the time, and increases mobility.The admixture is commonly used in from reinforced concrete.High scope diminishing is mixed Object is closed to may include：Melamine sulfonates polycondensation product, naphthalene sulfonate polycondensation product and polycarboxylate.

Middle range diminishing admixture is commonly used between so that the water content of cement composition is reduced by 5% and 10% without blocking The initial condensation time.Middle range diminishing admixture may include：The salt and polycarboxylate of lignosulfonic acid and they.

Such as BRP admixtures as described above can be liquid or solid composition.In the presence of in the form of liquid component, remove Except BRP components and compound ingredients, admixture may also comprise a certain amount of water.The amount of water is alterable, and in some cases Under, 20 to 95, in the range of 60 to 75wt%.In the presence of in solid form, the solid can be liquid compound Dehydrated form.Solid can be using for any suitable scheme from liquid removal water (such as free water), such as evaporation, freezing The solid that dry, freeze-drying etc. is generated from liquid compound.After being combined with the water of suitable volume, obtained solid is dissolved in the water To generate liquid compound for example as described above.In some cases, recovery is mixed by combined solid (such as freeze-drying) Object is closed with enough liquid (such as aqueous medium, such as water) to reach, wherein the ratio of liquid used and solid is alterable, and In some cases, 1,000,000 to 1, such as 10,000 to 1, including 5,000 to 1, such as 1,000 to 1, such as 500 to 1, packet It includes in the range of 100 to 1.Solid blend may include a variety of different grain sizes and size distribution.For example, in some embodiment party In case, solid blend may include size at 1 to 10,000 μm, such as 10 to 1,000 μm, and include 50 to 500 μm of range Interior particle.

Concrete is typically to be blended with standard proportional.During mixing with casting concrete, and not all cement alkali group Divide and be all consumed in cementing reaction, and therefore becomes after the concrete has hardened unreachable.Normal condition is in concrete During solidification, the cement basic component of 55-70% is consumed in cementing reaction.The cement of 30-45% it is concrete curing it After keep unreacted.When designing economy concrete mix and reducing the carbon footprint of concrete, concrete mix is set Cementing efficiency in meter is important feature, because cement is the largest component of carbon footprint.It can make this excessive unreacted height Alkaline cement component (introduces) with bicarbonate radical as additive/admixture (such as described above) in liquid or solution state Reaction, to cause early strength to increase by forming carbonate.In some cases, this cement for making mixture design Content reduces, to improve the cost and carbon footprint of concrete.In this way, cement more efficient can be used for concrete mix In design.Therefore, aspect of the invention includes low hydraulic cement (such as low OPC) cement formulations, wherein compared to suitable pair According to (the identical admixture not combined with BRP additives/admixture), given cement formulations may include 2% or less, such as 5% Or it is less, include the hydraulic cement of 10% or less (dry weight), wherein the preparation can still have compared to the control Identical or better intensity reaches and/or condenses property, such as when identical or enhancing intensity and/or identical or faster condensation Between.

BRP admixtures and their preparation are further described in the U.S. Provisional Application No. 61/ submitted on July 10th, 2013 In 844,808, the disclosure of the application is hereby incorporated herein by.

The aspect of the present invention further includes the condensable cement group prepared from BRP additives for example as described above and admixture Close object.Refer to the flowable composition prepared from cement and coagulating liq, wherein institute for " condensable cement composition " It states flowable composition and condenses into solid product after the preparation.The condensable cement composition of the present invention is from cement, condensation Prepared by the combination of liquid and BRP additives/admixture (such as described above), wherein the composition can further include a kind of or more The other components of kind, such as but are not limited to：Aggregate, chemical admixture, minerals admixture etc..After generation, flowable composition can With a variety of consistency, such as paste, plaster etc., the wherein variable viscosity of flowable composition, in some cases, 0 To 1000mPa*s, in the range of 2 to 100mPa*s.After one period since generation flowable composition, it can flow Dynamic composition condenses into solid product, and wherein this period is alterable, and in some cases, at 1 minute to 24 hours, such as In the range of 1 hour to 3 hours.The compressive strength of the solid product generated after flowable composition condensation can also change, Under some cases, in 1 to 20,000psi, in the range of 1000 to 5000psi, as measured using ASTM Test No.s C109. The product that composition is condensed into is characterized in that including one or more be not present in the substance for generating composition Mineral facies, such as be not present in originating the mineral facies in cement component.Cement for generating theme condensable cement composition It is summarized in more detail herein with other optional components (such as another coagulating liq, aggregate etc.).

Term " cement " as used herein refers to being condensed later simultaneously with coagulating fluid (such as aqueous solution, such as water) combination The particulate composition of hardening.The particulate composition that composition gives cement may include particle of various sizes.In some cases Under, given cement can by longest cross-section lengths (such as diameter in spheroidal particle) at 1nm to 100 μm, such as 10nm to 20 μm, And including the particle composition in the range of 15nm to 10 μm.

Target cement includes hydraulic cement.Term " hydraulic cement " as used herein refers to when mixed with coagulating fluid When conjunction, due to one or more water contents independent of mixture, and in aqueous environments be stable chemical reaction and The cement hardened.Therefore, hydraulic cement can harden under water or when being constantly exposed to moistening weather condition.Target water Hydraulic cement includes but not limited to the hydraulic of Portland cement (Portland cement), modified Portland cement and blending Property cement.

In some embodiments, cement is Portland cement or Portland cement admixture.Portland cement is to pass through Grinding crushes clinker come the hydraulic cement composition generated, is substantially by hydraulic calcium silicate and a kind of or more on a small quantity The material of the calcium sulfate composition as mutually grinding additive of kind form.Clinker is by including calcium and dioxy with predetermined ratio The material that the original stock of SiClx was sintered or was heated to the sintering generated when high temperature is made.Original for generating the mixture The example of material includes but not limited to lime stone and clay.In addition to portland cement clinker, (it is controlled limited amount calcium sulfate Setting time) and up to 5% accessory constituent also be included in Portland cement (as allowed by various standards).Such as by Europe Continent standard EN197.1 is defined, and " portland cement clinker is should be by least 2/3rds (in mass) calcium silicates (3CaO SiO₂And 2CaOSiO₂) composition hydraulic material, wherein rest part is by containing aluminium and iron-containing clinker phase and other compounds Composition.CaO and SiO₂Ratio be no less than 2.0.5.0 mass % " are not to be exceeded in content of magnesium (MgO).In certain embodiments In, Portland cement is to meet U.S. material test association (American Society for Testing of Materials the wave of ASTM C150 standards and specification (I-VIII types) (standard specification of ASTM C150- Portland cements)) Special orchid cement.ASTM C150 cover the Portland cement of eight types, respectively have heterogeneity, and according to those property Matter is subject to specific use.The Portland cement of eight type is：1 type (normal)；IA types (normal, air entrainment)；II types (medium sulfate resistance)；IIA types (medium sulfate resistance, air entrainment)；Type III (high early strength)；IIIA types are (high early Phase intensity, air entrainment)；IV types (low hydration heat)；And V-type (high-sulfate resistance).In some embodiments, Portland Cement can be white Portland cement.White Portland cement is selected by the iron oxide and magnesia only containing negligible quantity Raw material is made, and the iron oxide and magnesia are the compounds for giving normal portland cement grey.White Portland cement is logical It is thin often visible structure wall, panelling, terrazzo surface, plaster, cement paint, ceramic tile to be used for for building and/or beautiful purpose In slurry and decorative concrete.

In some embodiments, cement can be the hydraulic cement blended.Phrase " the hydraulic of blending as used herein Property cement " refers to the hydraulic cement composition for the cement material for including two or more types.It is used to form the water of blending The material of hydraulic cement includes but not limited to：Portland cement, blast furnace slag, flying dust slag, Silica fumes, calcination it is viscous Soil, pozzolanic materials, hydrated lime and combinations thereof.In some embodiments, cement can be to build by laying bricks or stones or mortar cement.It builds by laying bricks or stones It is hydraulic cement and one or more plasticity material (such as lime stones or water by Portland cement or blending with mortar cement Close or hydraulic lime) mixture made from cement.In certain embodiments, other materials, which also are included in, builds by laying bricks or stones or sand To adjust the property of cement in pulp-water mud, such as setting time, machinability, backwater and durability, such as follows in additive It is described in more detail in chapters and sections.

In some embodiments, cement component can be non-hydraulic cement.For " non-hydraulic cement ", refer to Hydrated product (composition formed when cement is mixed with coagulating fluid) cement not resistant to water.On-hydraulic water The example of mud includes gypsum, plaster and lime cement.Non-hydraulic cement can be mixed with other components of such as pozzolanic materials To cause them resistant to water, that is, cause them that there is the hydraulicity.

It is variable with the amount of the cement component of other groups of subassemblys when preparing condensable composition from cement according to the present invention Change.In some cases, the amount of cement component is 5 to 30, as in the range of 10 to 15, including 16 to 24wt%.

Target coagulating liq includes aqueous liquid composition, the water combined such as pure water or with one or more solutes.In root It is alterable with the amount of the liquid component of other groups of subassemblys when preparing condensable composition from cement according to the present invention.In some feelings Under condition, the amount of liquid component is 5 to 25, as in the range of 6 to 9, including 10 to 16wt%.

As outlined above, in condensable composition produced according to the present invention, make cement and coagulating liq component with for example BRP additives and/or admixture combination as described above.When preparing condensable composition from cement according to the present invention, with it The amount that it organizes BRP additives/compound ingredients of subassembly is alterable.In some cases, BRP additives/compound ingredients Amount less than 1 to 25, such as less than 1 to 9, including be less than in the range of 10 to 16wt%.

When preparing condensable cement composition according to aspects of the present invention, cement component, BRP additions can be made as needed Agent/admixture and optionally other coagulating liqs and one or more other groups of subassemblys.The other components of target include but not limited to Aggregate, other admixtures, strengthening ingredient, such as fiber-reinforced material, reinforcing bar (spiral) etc..

In some embodiments, aggregate can be used for generating theme condensable cement composition (such as when needing concrete When).Target aggregate is alterable, wherein the aggregate includes but not limited to：Sand, gravel, rubble etc..It is main when being combined with aggregate Topic condensable cement composition, which serves as, makes aggregate be bonded together to form the sticker of the construction material such as concrete.

Fine aggregate is the material for almost completely passing through No. 4 sieves (ASTM C125 and ASTM C33), such as silica sand. Coarse aggregate is the material being predominantly retained on No. 4 sieves (ASTM C125 and ASTM C33), such as silica, quartz, crushing Round marble, glass marble, granite, lime stone, calcite, feldspar, blanket sand, sand or any other persistence aggregate and its Mixture.Therefore, term " aggregate " as used herein broadly refers to many different types of coarse particles materials and fine Both grain materials, including but not limited to：Sand, gravel, rubble, slag and the concrete of recycling.It is included in theme condensable water The amount and property of aggregate in mud composition can be widely varied.In certain embodiments, the amount of aggregate can by cement component, The 25% to 85% of the total composition of both bicarbonate additive and aggregate composition, such as 40% to 70%, and include 50% To about 70% (w/w).

It any suitable scheme and/or equipment can be used to carry out group and be combined into theme condensable cement composition as described herein Various components (such as cement, BRP additive/admixture, optional other coagulating liqs, aggregate and/or admixture) can be formed Condense cement composition.In some embodiments, each individual components of condensable cement composition can be combined to generate institute Mixture is generated when stating condensable cement composition.In some embodiments, a part or complete for various components can be made in advance Portion is combined with each other, and condensable cement composition is then generated after combining all components.For example, can make coagulating liq with it is another One component, such as BRP additives/admixture mixing, then with cement mixing to generate condensable cement composition.In certain realities It applies in scheme, coagulating liq and another component, such as admixture can be made to combine, then mix the coagulating liq and other groups Divide to generate condensable cement composition.

Any common mixing device and/or method can be used in generating theme condensable cement composition.It is adoptable normal Rule cement mixing equipment example include but not limited to：Hobart mixers；Tilted cylinder mixer；Omni mixers； Henschel mixers；V-type blender；With Nauta mixers.Conventional vessel can also be used for mixing theme condensable cement composition Object, including such as bucket, basin, wheelbarrow.In the embodiment described in which, depending on the volume of mixture and property, component is mixed Conjunction can carry out by hand, such as by with shovel, trowel or glove hand mixing material.

The ratio of the liquid and dried ingredients that are combined to produce condensable cement composition can be based on the component of mixture Property and the required property of the cement composition of generation are changed.For example, in some embodiments, in mixture The ratio of liquid component and dried ingredients can be 1:1.5 until about 1:2, until about 1:2.5, until about 1:3, until about 1:3.5, Until about 1:4, until about 1:4.5, until about 1:In the range of 5 (w/w).

Cement, CO₂The combination of isolation cement additive and optional components causes to generate condensable cement composition.As above It is summarized, refers to the flowable composition prepared from cement and coagulating liq for " condensable cement composition ", wherein Flowable composition condenses into solid product after the preparation.After generation, flowable composition can have a variety of consistency, such as Paste, plaster etc., the wherein variable viscosity of flowable composition, in some cases, 0 to 1000mPa*s, such as 2 to In the range of 100mPa*s.After one period since generation flowable composition, flowable composition condenses into solid Body product, wherein this period are alterable, and in some cases, at 1 minute to 24 hours, such as 1 hour to 3 hours model In enclosing.The compressive strength of solid product generated after flowable composition condensation can also change, in some cases, 1 to 20,000psi, in the range of 1000 to 5000psi, as measured using ASTM Test No.s C109.

LOI or calcination loss are a kind of observing remaining non-calcination carbonate in the case of Portland cement, or The common analysis of remaining non-calcination fuel is observed in the case of the lime-ash of lime-ash (FA) like flying.LOI can also be applied to measure The CO of other materials and volcanic ash (such as blast furnace slag)₂Content.LOI analysis methods about cement are by ASTM C114 To determine, and continue at least 15 minutes to 950+/- 50 DEG C to be standardized by heating cement sample.Method is from cement Residual carbonate phase shift water removal and remnants CO₂, and attempt for making industry heating standardize, and keep gained cement equal One.Calcination loss can be measured to the final cement and concrete sample for using BRP additives/admixture for example as described herein (LOI).Small size is determined, the LOI using the hardened cement sample of BRP additives/admixture can be used for determining final material The amount of the carbon of isolation in material.In the case where larger volume is identified, using CO₂The maturing of isolation cement additive The LOI of sample may be utilized.The case where carrying out LOI measurement to the final cement composition containing BRP additives/admixture Under, in some cases, it is contemplated that LOI can in the range of 0 and 7.76%, and to final concrete carry out LOI measurement In the case of, in some cases, LOI can depend on the hardening in cement and concrete sample in the range of 0 and 25.1% The amount for the residual water and carbonate that period promotes.

Condensable cement composition as described herein is suitable for a variety of different applications, including as building or construct material Material.The specific structure that is applicable in of condensable composition of the present invention includes but not limited to：Road surface, building structure, such as building, The foothold of ground, highway/road, overline bridge, parking lot structure, brick/block wall and door, enclosure wall and electric pole.The present invention Mortar be suitable for for example constructing block (such as brick) being bonded together and filled gap between constructing block.Mortar also can be used The section residing for being compromised or corroding is had become in fixed or reparation existing structure, such as replacing original mortar.

Using theme condensable cement composition come when generating such as structure as described above, the method may include making Condensable cement composition is located in a certain place, such as building yard, mold etc.；And make the condensable cement composition Solid product is condensed into the place, wherein setting time can for example be changed as described above.

It is benefited from according to the cement composition of certain embodiments as described herein and is carbonated referred in the art as early stage Effect.As known in the art, early stage carbonating is happened at by deliberately fresh concrete being made to be exposed to CO₂, with early water When muddy water has unified generation carbonation reaction.When the concrete and CO of fresh mix₂When reaction, carbonation reaction and normal hydration Occur together.Carbonating quickly occurs, and facilitates comparatively dense and stronger concrete.Calcite help to intensity into Exhibition.In some cases, it is related to it to provide early stage carbonating for use bicarbonate additive for example as described herein Benefit.

As a kind of reduction release to the artificial CO in earth atmosphere₂Amount mode, theme condensable cement composition The artificial CO being also applied in separating building material₂.For example, subject methods can be used for trapping by industrial consumption fossil fuel Generated a large amount of CO₂, and the CO trapped₂The bicarbonate that then can be converted to be incorporated in condensable cement composition adds Add agent.In this way, the CO generated by industrial process₂Can the discharge gas of flue gas freely remove, and be incorporated on a large scale To reduce the CO in earth atmosphere in construction material₂Total amount.Therefore, subject methods and composition are provided and are reduced from industrial process The amount of carbon emission is carried out, and the carbon for disposing discharge in construction material by the way that the carbon of discharge to be incorporated to also is provided.

CO is used when generating such as condensable cement composition as described above₂Isolation cement admixture can be used for dropping The carbon footprint of low cement and concrete composition, and thus cement and concrete composition that carbon footprint reduces are provided.Carbon foot The cement concrete composition that mark reduces may include such as normal portland cement (OPC) component, but for example since there are carbonic acid Hydrogen salt additive has the carbon footprint reduced compared to concrete of such as OPC as cement component is only included.In some realities It applies in scheme, the cement and concrete composition that carbon footprint reduces may include derived from the fuel (such as fossil fuel) used by people Carbon.For example, the cement and concrete composition that carbon footprint according to aspects of the present invention reduces may include with CO₂Form The carbon discharged by the burning of fossil fuel.In certain embodiments, the present invention composition (such as carbon footprint reduce Concrete composition) in be isolated carbon include or mixtures thereof carbonate, bicarbonate.About the calculating of carbon footprint, cement or The carbon footprint of concrete can determine in the following manner：It is corresponding that every cubic yard of each component is multiplied by with its every pound of carbon footprint These values are summed it up, and add 10.560kg/yd by poundage³(by average 20 miles of the carbon footprint of one yard of concrete transportation).It closes In OPC components, it is assumed that by the average CO of Portland cement production release₂It is 0.86 ton of CO₂/ ton cement (such as California cement Weather action group is reported), each pound Portland cement has 0.86 pound of production carbon footprint.It is assumed that average transportation range is 100 miles, the transport footprint of each pound Portland cement is 0.016 pound, and total carbon footprint is every pound of OPC0.876 pounds of CO₂.For carbon The purpose that footprint calculates, conventional aggregate can be assumed to have 0.043lb.CO₂The carbon footprint of/lb. aggregates, and such as flying dust slag, The carbon footprint of the conventional supplement cement material (SCM) of slag etc. can be assumed 0.045lb.CO₂/ lb. routines SCM.Compared to Include the reference concrete of conventional aggregate (such as sand and/or rock) and the OPC as unique cement component, carbon of the invention foot The magnitude that the carbon footprint for the concrete composition that mark reduces reduces can be equal to or more than 25lb.CO₂/yd³Concrete, 50lb.CO₂/ yd³Concrete, 100lb.CO₂/yd³Concrete is more than 200lb.CO₂/yd³Concrete is more than 300lb.CO₂/yd³Concrete, More than 400lb.CO₂/yd³Concrete is more than 500lb.CO₂/yd³Concrete.It includes for example such as that these carbon footprints, which reduce available, The upper CO₂The concrete mix of isolation admixture is reached.In certain embodiments, carbon footprint of the invention reduces Composition be neutral carbon because they generally do not have carbon footprint (if any), as use example is as provided above Calculating guilding principle determined.The neutral carbon concrete composition of the present invention includes showing carbon footprint to be less than 50lb.CO₂/yd³ Concrete, such as less than 25lb.CO₂/yd³Concrete, including it is less than 10lb.CO₂/yd³Concrete is, for example, less than 5lb.CO₂/yd³ Those of composition.In some embodiments, neutral carbon composition shows carbon footprint 0CO₂/yd³Concrete or smaller, it is such as negative Property carbon footprint be less than (i.e. negativity is more than) -1lb.CO₂/yd³Concrete is less than -2lb.CO₂/yd³Concrete is less than -3lb.CO₂/ yd³Concrete is less than -4lb.CO₂/yd³Concrete is less than -5lb.CO₂/yd³Concrete.

In some embodiments, small carbon footprint concrete has notable negativity carbon footprint.In the embodiment described in which, group It is mixed that the negativity carbon footprint of conjunction object is smaller than (i.e. negativity is more than) -10, -25, -50, -100, -250, -500, -750 or -1000lb. Solidifying soil.To obtain the composition that carbon footprint reduces, removes and use CO for example as described herein₂Except isolation admixture, also may be used Using one or more such as U.S. Patent number 7,753,274；7,753,618；With other CO described in 7,815,880₂Isolation Property composition, such as cement, supplement cement composition, aggregate etc.；The disclosure is herein incorporated by reference this Text.

It is further described on April 1st, 2013 using the method and the product that is generated by it of BRP additives/admixture The U.S.Provisional Serial 61/807,230 of submission；The U.S.Provisional Serial 61/ that on May 3rd, 2013 submits 819,427；In U.S.Provisional Serial 61/844,808；The disclosure of the application is herein incorporated by reference this Text.

Such as BRP additives/admixture as described above may be present in external member, the external member may include one or more Other components.Therefore, aspect of the invention includes external member comprising optionally can be used for generating condensable cement with one or more BRP additives/admixture of other groups of subassemblys of composition, wherein other optional components described in target include but not limited to： Cement, concrete admixture, coagulating liq, other admixtures etc..The various components of external member may be present in independent container, or work as When needing, two or more different components can be incorporated in single container.For example, dry BRP additives/blending Object can merge in single container with cement, and be sold together with the independent container with coagulating liq.

In the external member including both liquid component and solid component, the ratio of liquid component and solid component (is expressed as The decade amount of weight based on the solid component in the weight divided by mixture with the liquid component in mixture) it can apparent group After closing each component, the required consistency of condensable cement composition and change, wherein ratio can 0.2 to 1.0, such as 0.3 to 0.6 In the range of.In certain embodiments, it is contemplated that the ratio for liquid and solid in the method can be 0.15 To 0.5, such as the external member in the range of 0.2 to 0.45.In some cases, such as being laid with consumer it uses, BRP additions Agent/admixture be exist in liquid form, and can at 1oz. to 55 gallons, such as 1 gallon to 15 gallons, and include 2 plus Volume in the range of logical sequence to 5 gallons exists.In said case, the amount of the dried ingredients in external member can 5lb. extremely 100lb., as the amount in the range of 25lb. to 50lb. exists.

In addition to above-mentioned component, theme external member can further include implementing subject methods for using the component of external member Specification.Illustrate that material is alternatively for the material that illustrates using cement composition, such as it can be provided for cement composition Object is ready to use in the Building technology and principle of specific application therein.Specification for implementing subject methods is usually recorded in suitable It closes in record media.For example, specification can be printed on base material, such as paper or plastics.Therefore, specification can wrap It plugs a page form to be present in external member, is present in the container of external member or its component (i.e. with packaging or the relevant component of inner wrapping) In label.In other embodiments, electronic storage data text of the specification to be present in suitable computer-readable store media Part form exists, and the media are such as portable flash drive, memory stick or card, CD-ROM, disk.In other embodiment party In case, practical illustration book is not present in external member, but is provided for obtaining specification from long-range source, such as by internet Means.One example of this embodiment be include that can watch residing for specification and/or can download the network address of specification from it External member.As specification, this means for obtaining specification are recorded in suitable base material.

Cement composition containing flying dust slag

Such as BRP compositions, additive and/or admixture as described above are suitable for the cement composition containing flying dust slag In and other application in.The composition be from BRP components (such as described above), cement component (such as described above) and Fly ash components to prepare.Term " flying dust slag " as used herein refers to the material generated by calcination coal, and includes the non-of coal Combustible mineral part.Flying dust slag generally comprises the spheroidal particle rich in silica, aluminium oxide and calcium, and is properly termed as F Two different classes of acquisitions of classification and C classifications.F classification flying dust slags are made by calcination anthracite and/or bituminous coal, and C classifications Flying dust slag is generated from lignite or subbituminous coal.The flying dust slag of any classification all can be used to prepare condensable together with subject methods Cement composition.

Flying dust slag can be used as the admixture in concrete to replace a part of Portland cement.Therefore, in certain embodiment party In case, the cement component for flying ash components and condensable cement composition can be made to blend.In some embodiments, flying dust can be made Slag is combined to produce with cement component flies ash components comprising 1 to 60 weight %, and such as 5 to 30 weight % fly ash components, including 10 to 20 weight % fly the admixture of ash components.

BRP components as described above can be together with the cement admixture including flying dust slag for overcoming containing flying dust slag Cement admixture one or more disadvantages (such as intensity obtain slowly, setting time it is longer).For example, theme carbon is combined Sour hydrogen salt component will produce with winged ash components than including flying dust slag, but the condensable cement composition without containing bicarbonate component Object more rapidly obtains the condensable cement composition of intensity and/or more quick setting.In the composition including bicarbonate component, In some cases, hardening time is faster by 3 to 70% than the composition for lacking bicarbonate component, and such as 5 to 30%, such as used ASTM C403 are measured.In some cases, composition had at 2 to 12 minutes, initial solidifying such as in the range of 2 to 7 minutes It ties time and at 4 to 15 minutes, such as the final setting time in the range of 8 to 15 minutes.In some embodiments, including The setting strength that the theme condensable cement composition of flying dust slag and bicarbonate component is reached is 500 to 3000psi, 7 in 3 days In it 3000 to 15000psi in 1000 to 8000psi and 28 days, as 28 days when 3500 to 8000 in the range of (as use ASTM C39 are measured).

When preparing condensable cement composition according to aspects of the present invention, cement component, BRP groups can be made as needed Divide, fly ash components and optionally other coagulating liqs (such as described above) and one or more other groups of subassemblys.Target its Its component includes but not limited to aggregate, other admixtures, strengthening ingredient, such as fiber-reinforced material, reinforcing bar (spiral) etc.. The material is described in further detail in the U.S. Provisional Patent Application No. 61/819,427 that on May 3rd, 2013 submits, the application Disclosure be incorporated herein in its entirety by reference.

In some cases, cement composition may include third cement component, so that it can be ternary composition.At some In the case of, in addition to flying dust slag and hydraulic cement component, third cement component can be slag cements.For slag cements, It refers to the cement for including grinding granulation blast furnace slag (GGBS or GGBFS).In some embodiments, slag cements component The 10 to 40 of total dried ingredients can be accounted for, such as 15 to 35, including 20 to 30 weight %.

Any suitable scheme and/or equipment can be used to combine the various of theme condensable cement composition as described herein Component (such as cement component, flying dust component, BRP components, optionally other coagulating liqs, aggregate and/or admixture) is to form example Condensable cement composition as discussed.

Such as the preparation and use of the cement composition as described above containing flying dust slag are described in further detail in August, 2013 In the U.S.Provisional Serial 61/866,988 submitted for 16th, the disclosure of the application is herein incorporated by reference this Text.

Carbonate is generated from BRP

After preparing BRP compositions (and its any storage as needed), in some cases, product can be a certain Mode is subject to further operating.For example, product or its component (such as LCP) can be operated to generate solid phase carbonate combination Object, and therefore by CO₂From initial CO₂Source is partitioned in solid form.The embodiment in some cases, make production Object or its component (such as LCP) are being enough to generate solid carbon with cationic source (such as one or more alkaline earth metal cation sources) It is combined under conditions of hydrochlorate composition.The cation of different valence mumbers can form solid carbonic acid salt composite (such as in carbonate mine Material form).In some cases, univalent cation can be used, such as sodium and potassium cationic.In other cases, two be can be used Valence cation, such as alkaline earth metal cation, such as calcium and magnesium cation.When addition cation to rich in bicarbonate radical product or When in its component (such as LCP), can the stoichiometric ratio of each one carbonate substance of cation generate carbonate solid (such as When bivalent cation includes Ca²⁺When amorphous calcium carbonate) precipitation.

Any Suitable cationic source can all be used in said case.Target cationic source includes but not limited to come from Generate the brine of the water processing establishment of the higher concentrate solution stream of cations, the facility such as seawater desalination factory, micro- salty Water desalination factory, groundwater reclaim facility, wastewater facilities etc..Also it is concerned with naturally occurring source as cationic source, such as But it is not limited to natural sea-water and geology brine, there can be different cation concns, and can also provide to trigger and be rich in certainly The product of bicarbonate radical or its component (such as LCP) generate the spare cationic source of carbonate solid.For the solid carbonic acid Salt generates the cationic source in step can be with the water for being for example rich in as described above in the product generation step of bicarbonate radical Property medium is identical or different.For example, the aqueous medium for being used to generate the product rich in bicarbonate radical can be that calcium cation is dense Degree is the natural sea-water of about 400ppm.Calcium cation concn is denseer cationic solution (Tathagata of twice of natural sea-water or more From the brine concentration object of seawater desalination factory) the second settling step can be then used to.

Or or in addition to introducing cation for example as described above, the other parameters of BRP compositions can be modified to promote It is precipitated into carbonate mine substance.For example, when BRP is pressurized compositions, pressure can be reduced to promote carbonate mineral The level that matter is precipitated from BRP compositions.In some cases, make pressure reduction 15psi or more, such as 150psi or more, and And in some cases, it is reduced to 2000 to 15psi, such as the value in the range of 200 to 14.8psi.

When needed, the property improved component may be provided in the BRP compositions for be subjected to solid carbonate deposition condition to come with certain Carbonate precipitation process is influenced for desirable mode is such as rate, the identity of product carbonate.For example, It may include the ion for influencing to form calcium carbonate from the solution rich in bicarbonate radical, such as chlorine ' onlooker ' ion.Alternatively, rich in The ion in the main body phase subregion between LCP and bulk solution phase in the product of bicarbonate radical can be used as catalyst for reaching It is separated into two kinds of liquid.Since the product rich in bicarbonate radical is rich in the property of bicarbonate radical, the ion of these other distribution Continuously forming for the various crystalline solid polymorphs of calcium carbonate can be further influenced, or inhibits to form other crystalline polymorphs Object.The operation of companion's ions of these distribution can be optimized to generate step in the product rich in bicarbonate radical (such as above It is described) period instructs the formation of LCP, and instructs noncrystalline or crystalline solid phase the growth of precipitation.Production rich in bicarbonate radical Which kind of influence property ion is the final use of object or its component can influence for the decision in the embodiment.For example, when When being used as the condensed medium of hydraulic cement rich in the product of bicarbonate radical or its component, using the property for not negatively affecting cement Influence ion.For example, sodium ion and chlorion can be avoided by as the influence ion in the embodiment.

In some cases, carbonate generation is carried out under conditions of LCP has residing.Therefore, carbonate, which generates, is Allow pH value existing for LCP (such as pH value 9.5 or smaller, as 9.3 or smaller) under carry out.

During generating solid carbonic acid salt composite from the product for being rich in bicarbonate radical or its component (such as LCP), for Every 2mol bicarbonate ions from BRLCP product compositions, can generate 1mol CO₂.For example, work as solid carbonate Composition is the generation of solid carbonic acid salt composite by adding in calcium cation to BRLCP product compositions come when generating, example As the formation of amorphous calcium carbonate minerals can be carried out according to following reaction：

Although the above reaction display generates 1mol CO₂, but come from and contain CO₂Source gas 2mol CO₂Initially it is converted At bicarbonate radical.Therefore, net 1mol CO are isolated in overall process₂, and be therefore a kind of effective CO₂Isolation technology, wherein above anti- There should be -37kJ mol^-1Descending standard state thermodynamics Energy distribution.

When needed, the CO generated during generating solid carbonic acid salt composite₂It can actively be removed from system for example to increase The generation of strong carbonate solid.By actively removing CO from system₂, similar to photosynthesis when being associated with calcification (as example In coral) carried out by, the above reaction can be forced towards right side, be thus conducive to the generation of solid carbonate.It can be used for certainly System removes CO₂Any suitable scheme.For example, CO₂It can be driven from solution into gas form, it is readily able to whereby From the liquid separation in system, and can be removed.It can be used any suitable scheme by CO₂In driving to gas form.? Under some cases, catalyst, such as carbonic anhydrase can be used, be both dehydratase and hydrase, and be especially responsible for CO₂It draws Go out blood to enter in lung with exhalation.When employed, the amount for the carbonic anhydrase being present in system will be enough to provide required activity, example Such as 10³To 10⁶s-¹, such as 10⁴To 10⁵s-¹In the range of activity.For generating CO from the liquid in system₂, and thus The another method for enhancing the generation of carbonate solid includes that the liquid in system is bubbled N₂Gas, this will drive CO₂, to Make HCO₃ ^-It is converted to CO₃ ^2-, and trigger solid carbonate (such as CaCO₃) precipitation.In some embodiments, addition such as Ca²⁺ Cation with from system remove CO₂The two is used equally for forcing solid carbonate from liquid precipitation.The side of these embodiments Method can be considered as every 2 moles of CO for being removed from gas stream₂, generate the CO of 1 mole of purifying₂Method, and thus can by regarding For by dilute flue gas be converted to concentration close to pure CO₂The method of logistics.

When for example making carbonate composition be precipitated from the product rich in bicarbonate radical as described above, product carbonate combination Object can greatly change.In some cases, product compositions are meta-stable carbonate compounds, molten after being combined with fresh water It solves and generates more more stable than the compound of initial precipitation product compositions different minerals matter in fresh water.Although (initial precipitation The compound of product compositions can dissolve after being combined with fresh water, then generate different component, but in any reaction, CO₂Gas does not discharge largely, or does not discharge completely in some cases).The compound of initial precipitation product compositions can be The compound more more stable in fresh water than them in brine, so that they can be considered as brine metastable compound.

Carbonate compound can be amorphous or crystallization.Specific minerals are distributed (i.e. in carbonate compound composition not The identity and respective amount of the different carbonate mine substances of same type) it is alterable, and by the water source being derived from depending on it Special properties and specified conditions for obtaining it.In certain embodiments, carbonate compound is in the form of small particles In the presence of such as wherein granularity is at 0.1 micron to 100 microns, such as 1 to 100 micron or 10 to 100 microns or 50 to 100 micro- Rice, in some embodiments in the range of 0.5 to 10 micron, as measured by scanning electron microscopy.In some implementations In scheme, granularity shows bimodal or multi-modal distribution.In certain embodiments, the high surface area that particle has for example exists 0.5 to 100m²/ gm, 0.5 to 50m²/ gm, such as 0.5 to 2.0m²In the range of/gm, such as pass through Blang's grace (Brauner), Ethylmercurichlorendimide Special (Emmit) and Teller (Teller) (BET) Surface area analysis is measured.In some embodiments, by the method for the invention The CO of generation₂Isolation product may include crystalline rods and amorphous solid.Crystalline rods are alterable in configuration aspects, and at certain In a little embodiments, have 500 to 1, such as the L/D ratio rate in the range of 10 to 1.In certain embodiments, brilliant The length of body is at 0.5 μm to 500 μm, in the range of 5 μm to 100 μm.In other embodiments, it generates generally completely non- Brilliant solid.

In some cases, the carbonate of precipitation has high reflector.Because material has high reflector, it Have high total surface reflectivity (TSR) value.Any suitable scheme can be used, as ASTM E1918 are used for in-site measurement water-glass The standard method of test of the Solar reflectance in face and low gradient surface come measure TSR (referring also to R.Levinson, H.Akbari, P.Berdahl,Measuring solar reflectance–Part II:review of practical methods, LBNL 2010).In some cases, material shows TSR values in Rg；0=0.0 to Rg；0 ,=1.0, such as Rg；0 ,=0.25 to Rg；0 ,=0.99, including Rg；0 ,=0.40 to Rg；In the range of 0 ,=0.98, for example, as using above by reference to scheme surveyed Amount.

In some cases, carbonate high reflection near-infrared (NIR) light of precipitation.Refer to wavelength for NIR light Light in the range of 700 nanometers (nm) are to 2.5mm.Any suitable scheme can be used to measure for NIR reflectance, and the scheme is such as The standard that ASTM C1371-04a (2010) e1 is used to measure emissivity of the material close to room temperature using portable emissivity instrument is surveyed Method for testing (http://www.astm.org/Standards/C1371.htm) or ASTM G173-03 (2012) direct motion it is normal With the standard in 37 ° of inclined surface epispheres with reference to spectrum of sunlight irradiation level table (http://rredc.nrel.gov/solar/ spectra/am1.5/ASTMG173/ASTMG173.html).In some cases, material shows NIR reflectance value in Rg；0 =0.0 to Rg；0=1.0, such as Rg；0=0.25 to Rg；0=0.99, including Rg；0=0.40 to Rg；In the range of 0=0.98, Such as using above by reference to scheme measured by.

In some cases, ultraviolet (UV) light of the carbonate high reflection of precipitation.Refer to that wavelength exists for UV light Light in the range of 400nm and 10nm.Any suitable scheme can be used to measure for UV reflectivity, the scheme such as ASTM G173- Normal and in 37 ° of inclined surface epispheres the standard reference spectrum of sunlight irradiation level table of 03 (2012) direct motion.In some cases, CO₂Insulation material shows UV values in Rg；0=0.0 to Rg；0=1.0, such as Rg；0=0.25 to Rg；0=0.99, including Rg；0 =0.4 to Rg；In the range of 0=0.98, for example, as using above by reference to scheme measured by.

In some cases, the carbonate of precipitation also reflects visible light.Refer to wavelength in 380nm for visible light Light in the range of to 740nm.Any suitable scheme can be used to measure for visible reflection properties, the scheme such as ASTM Normal and in 37 ° of inclined surface epispheres the standard reference spectrum of sunlight irradiation level table of G173-03 (2012) direct motion.In some feelings Under condition, CO₂Insulation material shows visible reflectance value in Rg；0=0.0 to Rg；0=1.0, such as Rg；0=0.25 to Rg；0 =0.99, including Rg；0=0.4 to Rg；In the range of 0=0.98, for example, as using above by reference to scheme measured by.

As outlined above, the carbonate of precipitation can be amorphous or crystallite.In some cases, material is crystallite.Work as material When being crystallite, such as the crystalline size as measured using the Scherrer formula of the FWHM applied to X-ray diffraction pattern is smaller, And in some cases, diameter is 1000 microns or smaller, if diameter is 100 microns or smaller, and include diameter is 10 Micron or smaller.In some cases, the diameter of crystalline size is in 1000 μ to 0.001 μ, such as 10 to 0.001 μ, including 1 to In the range of 0.001 μ.In some embodiments, the material generated by the method for the invention may include crystalline rods and amorphous Solid.Crystalline rods are alterable in configuration aspects, and in certain embodiments, have 500 to 1, such as 10 to 1 range Interior L/D ratio rate.In certain embodiments, the length of crystal is at 0.5 μm to 500 μm, such as 5 μm to 100 μm of model In enclosing.In other embodiments, generally completely amorphous solid is generated.

Density, porosity and the permeability of the carbonate of precipitation can vary depending on the application.About density, although material Density it is alterable, but in some cases, density is in 5g/cm³To 0.01g/cm³, such as 3g/cm³To 0.3g/cm³, and wrap Include 2.7g/cm³To 0.4g/cm³In the range of.About the porosity such as measured by Gas Surface Absorption, the gas surface is inhaled Attached is such as by BET method (Blang (Brown), Emmett (Emmett), Teller (Teller)) (such as such as in http:// En.wikipedia.org/wiki/BET_theory, S.Brunauer, P.H.Emmett and E.Teller, J.Am.Chem.Soc.,1938,60,309.doi:It is described at 10.1021/ja01269a023) it measures, in some cases, hole Porosity can be in 100m²/ g to 0.1m²/ g, such as 60m²/ g to 1m²/ g, and include 40m²/ g to 1.5m²In the range of/g.About can Permeability, in some cases, the permeability of material can be in 0.1 to 100 darcy, such as 1 to 10 darcy, including 1 to 5 darcy In range (such as used H.Darcy, Les Fontaines Publiques de la Ville de Dijon, Scheme described in Dalmont, Pari s (1856) is measured).Permeability also can be by the water absorption rate of assessment material come table Sign.As measured by water absorption rate scheme, such as in some embodiments, the water absorption rate of material 0 to 25%, such as 1 to 15%, and include in the range of 2 to 9%.The hardness of material can also change.In some cases, material shows Mohs' hardness (Mohs hardness) 3 or bigger, such as 5 or bigger, including 6 or bigger, wherein in some cases, hardness is in 3 to 8, such as 4 To 7, and in the range of including 5 to 6 Mohs degree (such as used Ame rican Federation of Scheme described in Mineralogical Societies. " Mohs Scale of Mineral Hardness " is measured). Hardness can also be for example as indicated using the tensile strength of the scheme measurement described in ASTM C1167.In some situations Under, material can show compressive strength 100 to 3000N, such as 400 to 2000N, including 500 to 1800N.In some cases, carbonic acid Salt composite shows second order or even three rank birefringences.

It can be seen that providing one kind with the reflectance spectrum art in near-infrared (0.35-2.55um) and being used to measure mineralogy and acquisition The quick, cheap of information, non-destructive technique about the minor element of carbonate mine substance and rock chemistry.Due to carbonate The spectrum of the vibration of group, all usually existing anhydrous end member's carbonate mine substances all contains in wavelength>Seven under 1.6um Strong absorption band.Interval between position, width and carbonate bands of a spectrum is mineralogical characteristic.Carbonate bands of a spectrum are in different minerals matter Spectrum between position difference be mainly due to dominant cation quality difference, wherein cation electronegativities rise secondary work With.The spectrum of calcite group minerals contains the Absorption Characteristics for being attributed to transition-metal cation (such as Fe and Mn), also may be used Minerals are contributed to identify.Spectrum confirms that two kinds of cations exist with divalent state.Fe²⁺The broad feature close to 1.1 μm is generated, Its position and dual degree are related to the size of octahedral site and degreeof tortuosity such as predicted by crystal field theory.Mn²⁺With Fe²⁺Extremely strong absorption band is generated in the minerals (being manganese spar and siderite respectively) that they are dominant cation, so that These easily distinguishable minerals and other carbonate mine substances, or even when the presence of water band may make it difficult to accurately determine carbonic acid When root band position.

The product of precipitation may include one or more different carbonate compounds, such as two or more different carbonations Close object, such as three or more different carbonate compounds, five kinds or more different carbonate compounds etc., including it is non-not Same, amorphous carbonate compound.The carbonate compound of the product of the precipitation of the present invention can be with molecular formula X_m(CO₃)_nChange Object is closed, wherein X is can to exist with the combination of carbonate group or any element or element of its multiple object chemical bonded refractory, wherein X It is alkaline-earth metal in certain embodiments and non-alkali metal；Wherein m and n is stoichiometry positive integer.These carbonate compounds There can be molecular formula X_m(CO₃)_n·H₂O, wherein there are one or more constitution waters in the molecular formula.Such as by using retouching It can be 40% or more to state and execute the amount of the carbonate in the product that coulometry measures by the scheme of coulometric titration, such as 70% or more, including 80% or more.

The carbonate compound of the product of precipitation may include many different cations, such as but ion object not limited to the following Matter：Calcium, magnesium, sodium, potassium, sulphur, boron, silicon, strontium and combinations thereof.It is contemplated that the carbonate compound of divalent metal, such as Calcium carbonate and magnesium carbonate compound.The specific carbonate compound of target includes but not limited to：Calcium carbonate mineral matter, carbonic acid magnesium mineral Matter and miemite minerals.Target calcium carbonate minerals include but not limited to：Calcite (CaCO₃), aragonite (CaCO₃), ball graupel Stone (CaCO₃), six hydroconite (CaCO₃·6H₂) and amorphous calcium carbonate (CaCO O₃).Target carbonic acid magnesium mineral matter includes but not It is limited to magnesite (MgCO₃), hydromagnesite (MgCO₃·2H₂O), nesquehonite (MgCO₃·3H₂O), five hydromagnesite (MgCO₃·5H₂O), hydromagnesite and amorphous magnesium carbonate calcium (MgCO₃).Target carbonic acid Calcium magnesium minerals matter includes but not limited to white clouds Stone (CaMg) (CO₃)₂), huntite (Mg₃Ca(CO₃)₄) and water huntite (Ca₂Mg₁₁(CO₃)₁₃·H₂O).The carbonic acid of product Salt compound may include one or more hydrate waters, or can be anhydrous.In some cases, the magnesium carbonate compound in precipitation Amount by weight be more than precipitation in carbonic acid calcium compound amount by weight.For example, the magnesium carbonate in precipitation The amount by weight of compound can be more than the amount 5% by weight of carbonic acid calcium compound or more in precipitation, such as 10% Or more, 15% or more, 20% or more, 25% or more, 30% or more.In some cases, the carbonic acid in precipitation The weight ratio of magnesium compound and carbonic acid calcium compound is in 1.5-5 to 1, in the range of 2-4 to 1, including 2-3 to 1.In some feelings Under condition, the product of precipitation may include hydroxide, such as bivalent metal ion hydroxide, such as calcium hydroxide and/or hydroxide Magnesium.

In some cases, it can be integrated by the method for making above method and power plant being made to cool down to enhance solid carbonate Compound generates and CO₂Gas generates.For example, make the aqueous medium of the buffered with bicarbonate of large volume (such as arrogant The water for the naturally occurring buffered with bicarbonate that ocean obtains) with original cigarette for example from power plant (Tathagata spontaneous combustion coal power plant) Road gas contact is to generate the product for being for example rich in bicarbonate radical as described above.Product of the gained rich in bicarbonate radical is then used to Cooling power plant, for example, using the product rich in bicarbonate radical as power plant water cooling system in coolant.In other words, Then the product rich in bicarbonate radical is made to pass through power plant to serve as the cooling water in power plant, this makes power plant cool down, but after making Hold the water heating in the technique in step.In said case, the temperature of the product rich in bicarbonate radical in cooling system is inputted Degree and can be at 5 to 100 DEG C, such as 10 to 100 by the temperature difference between the temperature of the product rich in bicarbonate radical of cooling system output DEG C, and include in the range of 20 to 100 DEG C so that into cooling system the product rich in bicarbonate radical temperature can- 1.4 to 50 DEG C, as in the range of -1.0 to 40 DEG C, and can be from the temperature of the product rich in bicarbonate radical of cooling system output 20 to 100 DEG C, in the range of 25 to 100 DEG C.The heating of product rich in bicarbonate radical makes CO₂Solubility drop in water It is low, to drive CO₂Gas, and reduce such as CaCO₃Carbonate compound solubility, lead to the compound precipitation.This A reaction can be by there are catalyst, such as enzyme, synthetic catalyst or the colloidal metal particles for accelerating reaction, such as previously discussed Carbonic anhydrase, transition metal nitrogen heterocyclic ring or colloidal transition metal particle further speed up.

In some cases, the original flue for the large volume that above method processing is generated by power plant (such as coal-fired power plant) The rate of gas can mutually be equal to the volume generated by the power plant.For example, 500MW coal-fired power plants can generate about every year 8000000 tons of CO₂, or about 20,000 ton of CO can be generated daily₂.Typical seashore power plant is recycled about 1,000,000,000 gallons of seawater daily, Or CO per ton₂About 50,000 gallons.50,000 gallons of seawater contains about 800kg Ca²⁺With 2,400kg Mg²⁺, or about 3, The total bivalent cations of 200kg.To form 1 ton of CaCO₃, need 440kg CO₂(or 600kg HCO₃ ^-) and 400kg Ca²⁺.Therefore, Seawater contains as by CO₂Trapping is in MgCO for 1 ton₃Or CaCO₃Ca needed for the carbonate mine substance solid of form more than twice²⁺ With the Mg more than six times²⁺。

In these embodiments, Ca²⁺Order of addition visually compared to the aqueous medium as buffered with bicarbonate Environment Ca in natural water²⁺Level, in front end, the product rich in bicarbonate radical generates the concentration for the bicarbonate radical reached in step, And CaCO₃It is preferred precipitation or preferably a certain other carbonate compounds (such as MgCO₃、CaMg(CO₃)₂Deng) and Variation.Seawater contains about 410mg/L Ca²⁺About 1200mg/L Mg²⁺, and the typical underground water from interior basin usually contains There are 2000-40,000mg/L Ca²⁺With less than 1000mg/L Mg²⁺.For example, if CaMg (CO₃)₂, dolomite or former white Marble is preferred carbonate mine substance, then seawater will be preferred raw material, and can need not be added containing Ca²⁺' hard water '. In CaCO₃It can be the inland place residing for preferred carbonate mine substance, contain high-caliber Ca²⁺' hard water ' can be rich in formation It is introduced as second step after the solution of bicarbonate radical.It is used as the upper of the coolant in power plant in the product rich in bicarbonate radical It states in embodiment, the product rich in bicarbonate radical generates reactor can be with the component part common location in power plant or power plant.

It includes the solid carbonate precipitated that can cause to generate from BRP precipitation solids carbonate composition for example as described above Composition and from its generation precipitation product remaining liq (i.e. mother liquor) the two composition.This composition can precipitate Exist with the slurry form of mother liquor.

This Product slurries can in a certain manner be disposed after it is generated.Phrase " disposition " refers to slurries or part of it (such as its solid carbonic acid salt composite part) is placed at storage place or be used to (manufacture or artificial in another product Article) in further use, wherein it by " storage " in that other products at least persistently that other products the expection longevity Life.

In some cases, this disposition step includes that above-mentioned serosity combination is transported to long term storage place.Storage Place can be ground place, underground or underwater place.In these embodiments, by slurries be placed on storage place it Afterwards, the mother liquor component of slurries can such as by evaporating, spreading come with precipitation natural separation.

When needed, the product (i.e. solid carbonic acid salt composite) that gained precipitates can be made to be detached with mother liquid obtained.It can be used Any proper method reaches the separation of solid carbonic acid salt composite.For example, drying solid carbonate composition can be passed through Reach separation to generate dry solid carbonic acid salt composite.Target drying proposal includes filtering precipitation from mother liquor to generate filter Liquid is then air-dried filtrate.When filtrate is air-dried, can be as needed by being air-dried by -70 to 120 DEG C In the range of at a temperature of.In some cases, drying may include slurries being placed on dry place (such as tailing pit), and make The liquid component of precipitation evaporates and leaves required dry product.Also it is concerned with freeze-drying and scheme (is lyophilized), wherein cold Freeze solid carbonic acid salt composite, reduces ambient pressure, and add enough heats so that the chilled water in material is directly from freezing Precipitated phase sublime up into gas.Another target drying proposal is spray drying, wherein being fed by the liquid that will contain precipitation The liquid is dried across hot gas, such as liquid feedback material is wherein pumped across sprayer and is entered in main hothouse, and Hot gas is passed through relative to sprayer direction in the form of cocurrent or countercurrent.

When making the product of precipitation be detached with mother liquor, the multitude of different ways that gained precipitation can illustrate further below adds With disposition.For example, precipitation can be used as the component of construction material, as summarized more fully below.Alternatively, precipitation can be placed At long term storage place (sometimes referred in the art as carbon storehouse), wherein the place can be ground place, underground or underwater (such as deep water) place.

In certain embodiments, refine and (handle) product carbonate combination in a certain manner before subsequent use Object.It is refined to may include a variety of different schemes.In certain embodiments, machine finish is subjected the product to, such as is ground, to obtain Product with required physical property (such as granularity etc.).In certain embodiments, make precipitation for example as complementarity cement Material, as sand, gravel, as aggregate etc. and hydraulic cement composition.In certain embodiments, it can add one or more To generate final product (such as concrete or mortar), described one kind in component to precipitation (such as wherein precipitating cement to be used as) Or various ingredients are such as one or more additives, sand, aggregate, complementarity cement material.

In certain embodiments, carbonate compound is for generating in aggregate, such as such as U.S. Patent number 7,914,685 Described, the disclosure is hereby incorporated herein by.In certain embodiments, carbonate compound precipitation Component as hydraulic cement.Term " hydraulic cement " is solidifying after being combined with water for referring on its conventional meaning The composition tied and hardened.The condensation and hardening for the product that cement by combining the present invention is generated with aqueous fluids are by generating After being reacted with water from caused by the hydrate that cement is formed, wherein the hydrate is substantially insoluble in.The carbonate chemical combination Object component hydraulic cement, their method of manufacture and use thereof include but not limited to described in U.S. Patent number 7,735,274 Those；The disclosure is hereby incorporated herein by.

Also the dissolving precipitation cement that is subjected to being dissolved in solution and be settled out alternative material, such as orthopedic phosphoric acid are concerned with Calcium cement.Dissolving precipitation cement is however the cement of ion storage cavern, storage cavern mediation will to be used as using solution without hydration It is compared to concrete, and the recrystallization of the relatively lower state material containing volume filler (such as aggregate and compared with fine aggregate).

Also it is concerned with the construction material of forming.The construction material of the forming of the present invention can greatly change.With regard to " forming " Speech refers to moulding (such as mould, casting, cut or in addition generate) into the physical form of artificial structure determination, i.e. configuration.At The construction material of shape be different from do not have determine and it is stable shaped, but instead comply with contain they container (such as bag or Other containers) amorphous construction material, such as particle (such as powder) composition.The construction material of illustrative forming includes but unlimited In：Brick；Plate；Pipe；Beam；Basin；Column；Drywall etc..The other examples and details of construction material about forming include the U.S. Those of described in published application US20110290156；The disclosure of the application is hereby incorporated herein by.

Also non-aqueous clay divine force that created the universe product of the product including the present invention as component are concerned with.The non-aqueous of the present invention clay is made Article can greatly change.For non-cement, refer to composition be hydraulic cement.Therefore, composition be when with such as Condensation is to generate the composition of the drying of stable product when the coagulating fluid combination of water.Illustrative composition includes but not limited to： Paper product；Polymerization product；Lubricant；Asphaltic products；Paint；Personal care product, such as cosmetics, toothpaste, deodorant, soap and washes Hair essence；People can absorb product, including both liquid and solid；Agricultural products, such as soil improvement product and animal feed；Deng.It closes In the other examples and details of non-aqueous clay divine force that created the universe product include those of described in U.S. Patent number 7,829,053；The patent Disclosure be hereby incorporated herein by.

In some cases, solid carbonate product can be used in albedo enhancing application.Albedo, i.e. reflectance factor, Refer to diffusing reflection or the reflectivity on surface.It is defined as the reflected radiation from surface and incident radiation on the surface Ratio.Albedo is dimensionless score, and is represented by ratio or percentage.Albedo be from zero (for complete black For the areflexia power on surface) to 1 (for white surface it is fully reflective for) scale on measured.Although albedo Depending on the frequency of radiation, but as used herein, albedo is provided under without reference to specific wavelength, and therefore refers to crossing over The average value of the spectrum of visible light (i.e. from about 380 to about 740nm).

When the method for these embodiments is the method for the albedo for enhancing surface, in some cases, method causes The magnitude that albedo increases (compared to suitable control, such as not being subjected to the albedo of the similar face of the method for the present invention) is .05 Or more, such as 0.1 or more, such as 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 Or more, 0.8 or more, 0.9 or more, including 0.95 or more, including up to 1.0.Therefore, the aspect of subject methods includes So that the albedo on surface is increased to 0.1 or more, such as 0.2 or more, such as 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 0.95 or more, including 0.975 or more, and up to about 1.0。

The aspect of method includes that target surface is made to associate with a certain amount of high reflector crystallite or non-crystalline material composition, The composition effectively makes the albedo on the surface enhance aequum, such as above listed amount.It can be used any suitable for side Case makes material compositions and the target surface associate.It therefore, can be by the way that material be incorporated to the object with surface to be modified Material compositions are made to associate with target surface in material.For example, when target surface is as roofing tile or concrete are mixed Can include the target for being present in object in the composition of material by material compositions when closing the surface of the construction material of object On surface.Alternatively, for example material compositions can be made to be located at least part target table by being coated with target surface with composition On face.When with material compositions coating surface, the thickness variable of the gained coating on surface, and in some cases, It can be in 0.1mm to 25mm, if 2mm is to 20mm, and in the range of including 5mm to 10mm.It is used for as high reflector pigment Application in paint and other coating (such as photovoltaic beats solar panel) is also of interest.

The albedo on a variety of surfaces can be enhanced.Target surface include culture and naturally occurring object at least partly Surface towards sky.The target person face of making a list includes but not limited to：Road, pavement, building and its component part, such as room Top and its component part (roof shingle) and side, runway and other man-made structures, such as wall, dam, monument, decorative object Deng.Naturally occurring target surface includes but not limited to：Such as seen in both forestization region and non-forestization region, non-plant Plant surface, water (such as lake, the ocean and sea) surface etc. changed in place.

Carbonate deposition compound as described herein and resulting composition are used in albedo enhancing application Method be further described in the U.S.Provisional Serial 61/793,661 and in August, 2013 that on March 15th, 2013 submits In the U.S.Provisional Serial 61/866,985 submitted for 16th；The disclosure of the application is herein incorporated by reference this Text.

It is mother liquid obtained to be also pocessed as needed.For example, mother liquor can be made to be back to the water of buffered with bicarbonate The source (such as ocean) or another place of property medium.

Above method can be executed using batch or continuous processing scheme as needed.For example, batch side can be used Case, wherein the product rich in bicarbonate radical is to be configured to make to contain CO₂Gas and aqueous medium be enough to generate rich in carbon It is generated in the first reactor contacted under conditions of the product of sour hydrogen radical.Product of the product rich in bicarbonate radical and sun can then be made Ion source is being configured to for example by making carbonate solid from the product precipitation rich in bicarbonate radical from rich in bicarbonate radical Product generate carbonate solid second reactor in combine.One example of the processing scheme of this type is illustrated in Fig. 4. In Fig. 4, the CO spontaneous power plant's flue stack obtained₂It is being enough to generate the production rich in bicarbonate radical with the water obtained from ocean It is combined in first reactor under conditions of object, the product may include LCP for example as described above.Then gained is made to be rich in carbon The product of sour hydrogen radical and divalent cation source (such as Ca²⁺Source) it is combined to produce solid carbonate and pure in the second reactor CO₂Gas.Then according to needing obtained solid carbonate and CO₂Gas is further in for construction material.

It detaching into the different continuous processings for individually preserving place, can adopt different from will be enriched in the product of bicarbonate radical With the continuously unidirectional system with gradient, middle and upper reaches or front end are CO₂It absorbs place (there are a little calcium), and downstream or rear Being the amorphous calcium carbonate (ACC) of stoichiometry at end (means Ca:CO₃Ratio is 1:1) or its analog, such as amorphous magnesium carbonate (AMC) or the former dolomite form that is suspended, wherein formed agglomerate liquid phase after calcium is injected to the injection continuously punctuated The centre of process.The advantages of this method is that it does not need different static separation methods, and instead allows to be rich in bicarbonate radical Product formed and by absorb at once remove to maintain for making CO₂Nouveaux riches are absorbed into solution and generated containing bicarbonate radical The thermodynamic driving force of product, and continue downstream to the chemistry meter of cation additions triggering solid carbonic acid salt composite Measure another place residing for the coring of phase.So that main body is molten from bulk solution removal bicarbonate ion by forming the second phase The ratio of carbanion and bicarbonate ion in liquid keeps higher, and to keep higher pH, this is advantageously used for reaching CO₂(gas) is transformed into CO₂The thermodynamic driving force of (dissolving).From CO₂(dissolving) is to HCO₃ ^-The conversion rates of (dissolving) can pass through Catalyst accelerates such as carbonic anhydrase for example as described above.

Effectiveness

Such as method present invention as described above is suitable for isolation CO₂, i.e. CO₂Isolation.Just " CO₂For isolation ", refer to Self-contained CO₂Gas (such as the gaseous waste stream generated by industrial plant) remove or detach a certain amount of CO₂, so that at least one Part CO₂It is no longer present in it and contains CO from its removal₂Gas in.The CO of the present invention₂CO is isolated in isolation method₂, and In some cases, from a certain amount of CO₂Generate stable storing CO₂Isolation product, so as to generate the CO of product from it₂Then It is isolated in that product.Stable storing CO₂Isolation product is by a certain amount of CO₂Stable storing form is merged into (as Upper storage or fittings storage stable form) so that CO₂No longer it is present in air or can be used as the gas in air in gaseous form The stable storing composition that body obtains.Therefore, CO is isolated according to the method for the present invention₂Cause to prevent CO₂Gas enters air, and Allow so that CO₂The mode long term storage CO of a part for air is not become₂。CO₂Isolation be in the case where not adding basicity, by with The reactions of lower favorable thermodynamics is reached.

Therefore, although being not added in alkali to system, CO occurs₂Isolation.In embodiments of the invention, according to above Equation, CO₂Isolation is to occur in the following manner：For two bicarbonate ions of every consumption, by 1mol CO₂Isolation In the carbonate that mineralizes, but discharge 1mol CO₂.This leads to every 2mol CO for being converted to bicarbonate radical₂For, pass through 1mol CO are isolated₂, and other 1mol CO are precipitated₂To reach net removal CO₂.Although generating 1mol products CO₂, but for certainly Initially contain CO₂Gas remove every 2mol CO₂, 1mol CO₂It is isolated, it is a kind of CO is isolated to generate₂It is feasible simultaneously And cost-effective mode.Although forming the CO that carbonate mineral confrontation is absorbed in every 2mol directly from bicarbonate ion₂And Speech directly generates 1mol CO₂, but this leads to that CO is isolated only₂It is added without external basicity.This result is that possible because Two CO₂Molecule can be from gas phase adsorption to dissolving phase, and is formed in bicarbonate buffer and is dissociated into two carbon at once The carbonic acid of sour hydrogen radical ion.In addition, the pure CO of product₂It can be for example used in other techniques as raw material, or work is recycled to returning In the input gas of skill.Therefore, aspect of the invention includes that the CO of purifying is generated from impure starting material₂The method of product.

System

The aspect of the present invention further includes for for example by implementing method as described above come self-contained CO₂Gas remove CO₂ System, such as small-scale device, processing workshop or factory.The system of the present invention, which can have, to be made it possible to implement specific objective life Any configuration of production method.In some embodiments, system of the invention includes：Containing CO₂Gas source；Aqueous medium Source；Be configured to make described to contain CO₂Gas contacted under conditions of being enough to generate BRP with the aqueous medium it is anti- Answer device.

The aqueous medium source of any suitable buffered with bicarbonate may comprise in systems.In certain embodiments, The source includes the structure of the input equipment (pipeline or pipeline such as since the ocean) with aqueous medium.As aqueous Jie When matter is seawater, source can be the input equipment with seawater communication, and the such as wherein described input equipment is from ocean Import in water to the pipeline or the hull of feedback expects pipe or ship of system land based, such as wherein system is a part for ship, Such as in the system based on ocean.

Containing CO₂Gas source it is alterable.Containing CO₂Gas source example include but not limited to will contain CO₂Gas guide to In a part for system, such as guide to the reactor for being configured to generate such as product rich in bicarbonate radical including LCP In pipeline, conduit or pipeline.By aqueous medium source and contain CO₂Gas source be connected to be configured to make contain CO₂Gas with The reactor that the aqueous medium of buffered with bicarbonate contacts under conditions of being enough to generate as above-mentioned the product rich in bicarbonate radical. Reactor may include any of many components, the component such as temperature regulator (such as be configured to heat water to institute Need temperature), for example for introduce enhancing bicarbonate radical generate reagent chemical addition agent component, mechanical agitation and physical agitation Mechanism.Reactor may include mediating CO as described above₂It is converted to the catalyst of bicarbonate radical.Reactor may also comprise permission One or more parameters are monitored, such as internal reactor pressure, pH, concentration of metal ions and pCO₂Component.

Reactor further includes the output means of delivery of the product rich in bicarbonate radical.In some embodiments, it exports defeated It send the component that tool can be configured to will be enriched in bicarbonate radical to transport to storage place, is such as injected to salt water bearing reservoir under earth's surface, uses In the tailing pit being disposed or in naturally occurring water body (such as ocean, sea, lake or river).In other embodiments In, the product that output equipment can will be enriched in bicarbonate radical is transferred to package station, such as being put into container and and the hydraulicity Cement is packed together.Alternatively, output equipment can will be enriched in bicarbonate radical product be delivered to can be configured to from be rich in bicarbonate The product of root generates the second reactor of solid carbonic acid salt composite (precipitating).

In some cases, system includes being configured to be further processed the product rich in bicarbonate radical, such as to dry Dry product carrys out combination product with one or more other components (such as cement additive) to be produced from the product rich in bicarbonate radical The second reactor of raw solid carbonic acid salt composite etc..The embodiment party of carbonate product is configured to generate for wherein reactor Case, the reactor include rich in bicarbonate radical product input equipment and to be enough to cause solid carbonic acid salt compound Cation is introduced into the input equipment of the cationic source (as previously discussed) in the product rich in bicarbonate radical by the mode of precipitation.When When needing, this reactor can operationally be configured to the carbonate mine substance composition of precipitation is made to detach with mother liquor Separator is combined, and the composition and mother liquor are to be generated in the reactor from the product rich in bicarbonate radical.In certain embodiment party In case, separator can be such that the carbonate mine substance composition of precipitation is detached with mother liquor by mechanical means to reach, such as wherein Carry out autoprecipitation in the following manner and discharges a large amount of excessive waters：By gravity or addition vacuum, mechanical presses, from mother liquor filter precipitation with Generate filtrate, centrifugation or gravity Shen drop precipitation and discharge mother liquor.System may also comprise washing station, in the washing station, come It is washed from the precipitation of separator being largely dehydrated, such as salt and other solutes are removed with autoprecipitation, then carried out in dry station It is dry.In some cases, system further includes for the dry carbonate mine for precipitating the precipitation that station generates by carbonate mine substance The dry station of composition of matter.Depending on the specific drying proposal of viewing system, dry station may include filter element, freeze-drying knot Structure, spray-dried structure etc., it is such as above more fully described.System may include being connected to the defeated of drier since the industrial plant Device (such as conduit) is sent, so that gaseous waste stream (i.e. industrial plant flue gas) can directly connect in drying stage with moistening precipitation It touches.The precipitation of gained drying can be further processed (such as grind, mill) to obtain required physical property in refined station. When precipitation is used as construction material, one or more components may be added to that in precipitation.

System can further include allow from one of the following or it is multiple remove precipitation outlet conveyor (such as conveyer belt, Slurries pump)：Reactor, dry station, washing station or refined station.The product of precipitation reaction can be disposed in many different ways. Precipitation can in may include both aboveground storage facility and underground storage facilities empty transport carriage (such as barge, train, compartment, Truck etc.) in be transported to long term storage place.In other embodiments, precipitation can be disposed in place under water.It can adopt With for composition to be transported to any suitable scheme to disposal site.In certain embodiments, pipeline or similar can be used Slurries structure for conveying, wherein these methods may include actively pumping, gravity induced flow etc..

In certain embodiments, system will also include the website that the construction material such as cement is prepared for autoprecipitation.This A website can be configured to autoprecipitation and generate various cement, aggregate or cement material, such as in U.S. Patent number 7,735,274 It is described；The disclosure of the application is hereby incorporated herein by.

The continuous product reactor for being rich in bicarbonate radical

When generating the composition for being for example rich in bicarbonate radical as described above, carbon dioxide (CO₂) source and water phase can In product (BRP) reactor continuously rich in bicarbonate radical, (it can be for combination under conditions of being enough to generate required BRP compositions Such as single-stage reactor or multistage reactor as described below) in.

In some cases, by CO₂Source and water phase and it is other needed for component (such as LCP accelerating agents, catalyst, stabilization Agent etc.) it is introduced into flow reactor (it can be single-stage or multistage for example as described below), wherein reactor condition is enough reflexive Object is answered to generate BRP compositions.Refer to unidirectional for " continuous " reactor, and there is CO₂Source, water phase and LCP promote The upstream or front end that are introduced into agent and the reactor from the downstream of its acquisition BRP composition or rear end.Successive reaction Device can be considered as the reactor with gradient, and the BRP contents that middle and upper reaches or front end have are less than the BRP in downstream or rear end Content.When reactor is flow reactor, it is not batch reactor.Therefore, it is not the reactor for including single container, Composition of the container inside the container reaches stable state.

Reactor condition (it can change in multistage reactor from level-one to next stage) is enough from input CO₂, water phase and LCP accelerating agents generate BRP compositions.Any suitable scheme can be used to make to contain CO₂Gas is contacted with water phase.For example, mesh Marking contact scheme includes but not limited to：It is in direct contact scheme, such as the aqueous medium bubbled gas across certain volume；Cocurrent connects The scheme of touching, i.e., contact between the gaseous stream of one-way flow and liquid phase stream；Counter-current configuration, i.e., in the gas gas-phase objects of reverse flow It flows and is contacted between liquid phase stream.Contact can by using such as can be suitable injector, bubbler, fluid venturi react Device, sprinkler, pneumatic filter, sprayer, column plate or filling tower reactor etc. are reached.When LCP accelerating agents are different from water phase When, any suitable scheme can be used to make LCP accelerating agents and water phase and CO₂It combines in source.For example, these groups in independent source Dividing can be respectively respectively fed into the upstream position of reactor.Alternatively, two or more components can introduce reactor at them In before be combined.For example, CO₂Source and water phase can be combined before they are introduced into reactor.When water phase is When water phase including LCP accelerating agents, in these components all three will all be subject to group before they are introduced into reactor It closes.

It when needed, can be to reactor (or in multistage reactor, at least level-one) pressurization.For pressurization, it is Refer to the atmospheric pressure that the internal pressure of reactor (or at least its pressurized part) is more than reactor location.Therefore, in some feelings Under condition, CO is combined under stress₂Source；Water phase；With liquid condensation phase (LCP) accelerating agent.Although at the pressing position of reactor Pressure is alterable, but in some cases, and pressure is 50psi or higher, such as 75psi or higher, including 100psi or higher, Under some cases, 50 to 500psi, in the range of 75 to 250psi.Variable temperatures in reactor, and at some In the case of, at 0 to 100 DEG C, such as 20 to 80 DEG C, and include in the range of 40 to 70 DEG C.In some cases, the pH of reactor 8 to 9, as in the range of 8 to 8.5, including 8.3 to 8.5.

When needed, reactor can be configured to electric power promotion CO₂Isolation substance, such as bicarbonate, carbonate etc. Generation and/or stabilisation.For example, reactor may include that one or more autoreactors that are configured to remove H⁺, and Thus the cathode construction for promoting bicarbonate and/or carbonate to be formed.When using the reactor, method may include to be enough Promote CO₂The content electric power of the mode autoreactor of the generation of isolation substance removes H⁺。

When needed, scale preventative may include in the reactor for example to reduce or inhibit non-in reactor and/or pipeline Intentional property precipitation.Any suitable scale preventative can be used, wherein the reagent includes but not limited to：Scale removal chemical substance, such as day Winter propylhomoserin, poly-aspartate, glutamic acid, polyglutamic acid, acrylic acid, polyacrylic acid, hydrochloric acid or above-mentioned chemical substance Salt, i.e. aspartate etc..In some cases, scale preventative also acts as LCP accelerating agents as described above.

In some cases, the aspect of method includes generating required BRP compositions and non-BRP compositions.Non- BRP is combined Refer to by the group division object in initial input reactor, wherein the component is not present in final BRP compositions for object In.The variable constituents, and can be ion, water, solute etc..In the embodiment described in which, reactor can be configured to base The component of reactor is separated into BRP and non-BRP compositions in one or more features, wherein the feature includes but not limited to One of the following is multiple：Size, charge, viscosity, density, pH, solute composition etc..

In some cases, separation is reached using selective ion isolation.In some embodiments, it is used for method In reactor may include being configured to facilitate the first area selectively transports of one or more ion autoreactors to reacting The selective ion separator of the second area of device.In this way, selective ion separator can for example be used for comfortable reaction The BRP compositions generated in device detach non-wanted ion.

In some embodiments, selective ion separator is the ion separator based on charge, based on charge point From reactive component.For example, in some embodiments, selective ion separator includes close in the outer wall of reactor The electrically charged material of surface placement.Electrically charged material can be taken positively or negatively charged.In some embodiments, it is based on The ion separator of charge carries the positive charge of the outer wall attraction anion of orientating reaction device.The outer wall of anion orientating reaction device Anion concentration in the mobile region close to outer wall for leading to reactor increase and the central area of reactor in it is cloudy from Sub- concentration accordingly reduces.

In some embodiments, the ion separator based on charge includes carrying to repel come the moon of the outer wall of autoreactor The material of the negative electrical charge of ion.The center movement of anion orientating reaction device causes the anion in the central area of reactor dense Anion concentration in the region close to outer wall of degree increase and reactor accordingly reduces.

Any of a variety of suitable materials can be used for the ion separator based on charge, and the material includes but not limited to Ion exchange material, such as ion exchange resin, zeolite.The example of ion exchange resin includes：Including such as sulfonic acid group Highly acidic resin, such as kayexalate or poly- (2- acrylamidos -2- methyl-1s-propane sulfonic acid)；Including such as carboxylic acid The weakly acidic resin of group；Including such as quaternary ammonium, such as the basic resin of trimethyl ammonium group；And including such as primaquine The weakly base resin of base, secondary amino group and/or tertiary amino, such as polyethyleneimine.

In some embodiments, the ion separator based on charge can be placed in positioned inside reactor, and by with Set in the holding structure to keep the ion separator based on charge or on.In some embodiments, holding structure is located at anti- Near the inner surface for answering the outer wall of device.In some embodiments, the inner surface of the outer wall of holding structure autoreactor is to reaction The center of device extends, and the guarantor between the outer surface of the inner wall of the inner surface and holding structure of the outer wall with defined reaction device Hold the inner wall in space.In certain embodiments, the inner wall of holding structure includes large pore material layer, such as diameter macropores film, It allows fluid and molecule passes freely through the film, while the ion separator based on charge being maintained at and is kept in space.? In the embodiment, the content of reactor can pass freely through the inner wall of holding structure with the ion separator based on charge Interaction.In some embodiments, holding structure can be separated with reactor, be may be, for example, and be can be placed in inside reactor Independent structure.In the embodiment described in which, holding structure and reactor usually have same shape, and the size of holding structure It is such that holding structure can be placed on inside reactor.In some embodiments, holding structure can be placed on instead It answers inside device, and reactor can be movably attached to.

In certain embodiments, selective ion separator may be based on the ion separator of size comprising will be anti- The interior section of device is answered to be divided into the physical arrangement of at least two different zones.When in use, the selective ion based on size Separator allows the first area (such as region containing BRP compositions) of a certain ion autoreactor to reach the second of reactor Region (such as region of the non-BRP compositions or product containing reaction), while preventing other ions and/or molecule from passing through film. In this way, BRP compositions can be detached with unwanted reactive component.

In some embodiments, the ion separator based on size includes that the molecule under a certain size is allowed to pass through, Prevent the selective membrane that bigger molecule passes through simultaneously.In this way, the ion separator based on size can be used for being more than certain The molecule selective retention of one size is in the desired zone of reactor.In some embodiments, selective membrane includes size At 1 micron until about 2 microns, until about 3 microns, until about 4 microns, until about 5 microns, until about 6 microns, until about 7 micro- Rice, until about 8 microns, until about 9 microns or until hole in the range of about 10 microns or bigger.In the embodiment described in which, Film serves as the simple dimensions exclusion filter for preventing the molecule of a certain size from passing through fenestra.

In some embodiments, selective membrane may include size at about 1 angstrom (Angstrom) until about 10 angstroms, until about 20 angstroms, until about 30 angstroms, until about 40 angstroms, until about 50 angstroms, until about 60 angstroms, until about 70 angstroms, until about 80 angstroms, until about 90 angstroms, until about 100 angstroms, until about 200 angstroms, until about 300 angstroms, until about 400 angstroms, until about 500 angstroms, until about 600 angstroms, Up to about 700 angstroms, until about 800 angstroms, the hole in the range of about 900 angstroms or bigger.In some embodiments, selectivity Film include have size at about 5 angstroms until about 6 angstroms, until about 7 angstroms, until hole in the range of about 8 angstroms reverse osmosis membrane.It is described Film can not usually be permeated by ion, but hydrone is allowed to pass through film.

In some embodiments, selective membrane may include having size at about 1 nanometer until in the range of about 2 nanometers The NF membrane in hole.The film can be used for by allowing hydrone to pass through film, and retain Ca²⁺And Mg²⁺Ion makes such as Ca²⁺ And Mg²⁺Ion is separated from water.

In some embodiments, selective membrane may include with size at about 10 nanometers until about 20 nanometers, until about 30 nanometers, until about 40 nanometers, until about 50 nanometers, until about 60 nanometers, until about 70 nanometers, until about 80 nanometers, until About 90 nanometers, until about 100 nanometers, until about 125 nanometers, until about 150 nanometers, until about 175 nanometers, until about 200 receiving The ultrafiltration membrane in the hole in the range of rice or bigger.The film can be used for by the way that bigger molecule to be retained on the first side of film, together When allow solution so that bigger molecule is detached with solution across film.

Theme selective membrane can be placed in any suitable support construction.For example, in some embodiments, select Property film may include the material layer with pore size needed for as described above, and can be placed in support construction (such as macropore support Layer) on, wherein including to wait for that the solution of the molecule detached by selective membrane can pass freely through macropore supporting layer.

As discussed above, in some embodiments, the ion separator based on size can be by the inside portion of reactor It is divided into the physical arrangement of at least two different zones, wherein each region (such as is selected by the ion separator based on size Property film) with another region separate.In some embodiments, the ion separator based on size, which can be placed in, can be mounted on reaction On the column casing component of required position inside device or in reactor is divided at least two different zones.For example, exist In some embodiments, the ion separator based on size can be configured to be mounted on inside reactor with by the inside of reactor It is divided at least two different zones separated by the ion separator based on size.

In some embodiments, reacting precursor can be introduced into the first area of the reactor divided, so that precursor is deposited It is on the first side of the ion separator based on size.Because precursor inside reactor react, based on size from Molecular separator can be used for the various reactive components of Selective Separation.For example, in some embodiments, the non-BRLCP of reaction Component can be transported through by selectivity or across the ion separator based on size, and BRLCP components can be retained in based on size Ion separator the first side on.

In some embodiments, the ion separator based on size can be in the pipe sample with first end and second end Structure type.Pipe spline structure can be placed in inside reactor so that aperture fluid in first end and the first end of reactor Unicom, and the aperture fluid communication in second end and the second end of reactor.The wall of pipe spline structure includes being based on size Selective ion separator, such as film.The interior zone of pipe spline structure is by the wall of pipe spline structure and remaining inside portion of reactor Separate, and forms filter chamber.In some embodiments, reacting precursor can be introduced directly into the inside of pipe spline structure, It is introduced into filter chamber, in the inside, they are reacted to form BRP compositions.

In some embodiments, subject methods are related to combining with non-BRP to detach BRP compositions based on charge differences Object.For example, BRP entities needed for BRP compositions usually have neutral charge, and therefore not with other electrically charged points Son interaction.On the contrary, unwanted entity can be electrically charged in BRP compositions, wherein the entity may include such as chlorion, Sodium ion, potassium ion etc..Therefore, the isolation technics based on charge can be used for detaching BRP compositions and non-BRP compositions.

In some embodiments, the separation of BRP compositions and non-BRP compositions be by make the content of reactor with The electrically charged material (such as ion exchange resin) being placed in reactor contacts to reach.In certain embodiments, Electrically charged material is placed in holding structure as described above.Reactor content is moved freely in holding structure, In the holding structure, they contact electrically charged material.In some embodiments, electrically charged material carries positive electricity Lotus, and the non-BRP compositions (such as chlorion) with negative electrical charge are associated with electrically charged material.This leads to the center of reactor Chlorine ion concentration in region reduces.BRP compositions with small electric lotus do not associate with electrically charged material.Due to electrically charged Material and non-BRP compositions between selectivity interact, the non-BRP composition concentrations drop in the central area of reactor It is low, to allow to detach BRP compositions with higher degree.

In some embodiments, subject methods are related to combining with non-BRP to detach BRP compositions based on size difference Object.Theme BRP compositions are typically larger than non-BRP compositions in terms of size, and therefore can be used size selection component (as having Have the film of determining pore size) it is detached.

In some embodiments, BRP compositions are formed in the filter chamber in the first area of reactor.Filter chamber Wall include the film with determining pore size.Cross-film applies pressure difference, and the entity of BRP compositions is (such as shown in Fig. 3 Two tooth entities) size that has is more than fenestra, and therefore cannot pass through film.On the contrary, the ruler that the entity of non-BRP compositions has It is very little to be less than fenestra, and therefore pass freely through film.Due to transmembrane pressure, filters indoor BRP composition concentrations and increase, and mistake Filtering indoor non-BRP entities concentration reduces.In this way, BRP compositions can be detached with higher degree with non-BRP compositions.

As mentioned above, the reactor being used in the method for the present invention can be single-stage reactor or multistage reactor.Single-stage is anti- The schematic diagram of device is answered to be shown in Fig. 5.In Figure 5, CO will be contained₂Gas stream (such as flue gas) and water phase (such as brine) draw In the front end or upstream end that enter single-stage flow reactor.Brine further includes for example promoting in calcium ion and the LCP of magnesium ion form Agent.There is also counter ions, such as chlorion.Single-stage reactor be configured to include outer wall and inner tubular size separation (such as Nanofiltration) film pipe.The inside of reactor is for example forced into pressure in the range of 100 to 250psi.When in reactor When inclusion reaches rear end or downstream from front end or upstream end, BRP compositions are formed inside tubular film, and such as sodium ion and chlorine The non-BRP entities of ion pass through film.Then make required BRP compositions and non-BRP entity separations.Then the rear end of autoreactor or Downstream obtains BRP compositions.

In some embodiments, using multistage BRP reactors.For multistage, refer to reactor include two or More difference classification, wherein each downstream hierarchy with it close to upstream be classified communication.Different condition may be present in not With in classification.For example, different classifications may include different resolution elements, different catalysts, difference BRP accelerating agents, stabilizer Deng.In some embodiments, two different classifications are configured to carry out the aitiogenic different aspects of BRP.For example, exist In some embodiments, first reactor forms BRP compositions and non-BRP compositions for autoreaction precursor, and second reacts Device is for detaching non-BRP compositions and BRP compositions.In some embodiments, subject methods are related to through multiple reactors Continuous processing reactive component is classified to increase the bicarbonate radical content of BRP compositions, and/or real to remove a greater amount of non-BRP Body is so that BRP compositions can be detached with high carbon acid hydrogen radical content and/or high-purity.

Fig. 6 provides the embodiment according to the present invention executed in multistage, and specifically in two-stage reactor The schematic diagram of method.In figure 6, CO will be contained₂Gas stream (such as flue gas) and water phase (such as brine) introduce two-stage it is continuous In the front end or upstream end of the first order of reactor.Brine further includes the LCP accelerating agents for example in calcium ion and magnesium ion form. There is also counter ions, such as chlorion.The first order of reactor be configured to include outer wall and inner tubular size separation (such as Nanofiltration) film pipe.The inside of reactor is for example forced into pressure in the range of 100 to 250psi.When in reactor When inclusion reaches rear end or downstream from front end or upstream end, the first BRP compositions are formed inside tubular film, and such as sodium ion Film is passed through with the non-BRP entities of chlorion.Then by the first BRP compositions and optional divalent cation (such as Ca²⁺) be concomitantly introduced into In the second level of reactor.The second level of reactor is also configured as including outer wall and inner tubular size separation (such as ultrafiltration) The pipe of film.The inside of reactor is for example forced into pressure in the range of 100 to 250psi.When the second level of reactor When the front end of the second level of content autoreactor or upstream end reach rear end or downstream, it is small that LCP is formed inside tubular film The 2nd BRP compositions that content is higher than the first BRC compositions are dripped, and as the non-BRP entities of hydrogen ion and chlorion pass through film.It connects It the rear end of the second level of autoreactor or downstream obtains the 2nd BRP compositions of gained.

Fig. 7 provides the diagram of the method for embodiment according to the present invention, and wherein BRLCP product compositions are further used for Generate carbonate mine substance product as described above, such as CO₂Isolation carbonate mine substance.Method in Fig. 7 includes Fig. 6 All steps of the method for middle explanation.As shown in Figure 7, the final BRP product compositions that the second level of autoreactor obtains are handled Object is to generate carbonate mine substance.In this step, the pressure of BRP is made for example to be reduced to 200 to 14.8, such as 30 to Value in the range of 14.8psi.In doing so, calcium carbonate is settled out from BRP compositions.In addition, generating pure CO₂, can quilt Trapping is stored or is used then according to needs.

Fig. 8 provides the schematic diagram of the third-stage reactor of an embodiment according to the present invention.As shown in Figure 8, CO will be contained₂ Gas stream (such as flue gas) and water phase (such as brine) introduce under stress three-level flow reactor the first order front end Or in upstream end.The first order includes R.O. films.The filtrate of the first order is low pH liquid.Retentate is high pH brine.Then make stagnant It includes the second stage reactor of N.F. films to stay object arrival, and the film removes the ion of such as Na+, Cl- from input liquid selective It is rich in Ca to generate high pH²⁺, bicarbonate radical the water with LCP.Then this retentate is made to reach the third level for making LCP concentrate U.F. membrane reactor.The LCP of third level acquisition finally concentrated of autoreactor is handled to generate carbonate mine substance.

The aspect of the present invention includes that continuous BRP generates reactor and includes the system of the reactor.One system is to include Operationally (such as carbonate mine substance generates reactor with one or more as described in more detail below other functional units Deng) associated with BRP generate reactor device.

Target BRP generates reactor and is configured to composite reaction precursor (including such as CO₂Gas, aqueous medium and one Kind or plurality of liquid condensed phase (LCP) accelerating agent), and make the precursors reaction to generate the reactor of BRP compositions.At certain In a little embodiments, theme BRP is generated reactor and is configured to be operated with Sequential Production, so that reactor autoreaction precursor Continuously generate BRP compositions.

Theme BRP generates reactor and may include at least one slim-lined construction with first end and second end.It is elongated Structure can be hollow, and include the solid in the interior zone for wherein making reacting precursor combination and reaction of defined reaction device Wall.The visual many different variables of the overall length and width of structure and change, the variable such as needed for BRP generate scale, The amount and type of reacting precursor used, specific operation condition etc. to be employed.In some embodiments, BRP generates reactor Length 1 to 200ft, if 20ft is to 80ft, and in the range of including 27.1ft to 31.0ft.When reactor is multistage anti- When answering device, length at different levels is alterable, and in some cases, in 2ft to 400ft, if 10ft is to 200ft, and includes In the range of 54.2ft to 62.0ft.The width (such as diameter) that BRP generates reactor can also change, and in some embodiment party In case, in 1in. to 120in., if 3in. is to 60in, and in the range of including 12in to 24in..When reactor is multistage anti- When answering device, variable-width at different levels, and in some cases if 6in. is to 120in., and is wrapped in 2in. to 240in. In the range of including 24in to 48in..Therefore, the volume of reactor can also change.In some cases, the total volume of reactor exists 0.02ft³To 125ft³, such as 1ft³To 80ft³, and include 10.9ft³To 20.5ft³In the range of.When reactor is multistage anti- When answering device, variable volume at different levels, and in some cases, in 0.04ft³To 250ft³, such as 2ft³To 160ft³, and Including 21.8ft³To 41.0ft³In the range of.

BRP generates reactor and its cross-sectional shape of classification can also change.In some embodiments, BRP generates anti- It is typically cylinder to answer device, and has circular cross sectional shape.In other embodiments, theme reactor may include other Cross-sectional shape, including such as ellipse, square and/or rectangular cross-sectional shape.

Theme reactor is typically by suitable for containing the aitiogenic rigidity of BRP, non-reaction during the operation of reactor Property material structure.It includes but not limited to metal and metal alloy (such as stainless steel, low-carbon alloy steel), pottery to be suitble to the example of material Porcelain, glass, aggregation group are graded.In some embodiments, theme reactor can be polymerize by composite material, such as fibre strengthening The structures such as object, metal composite, ceramic complexes.

Theme BRP generates reactor and may include first end and second end.In some embodiments, first end quilt It configures to receive various reacting precursors, such as contains CO₂Gas, aqueous medium and/or other reactive components, it is such as a kind of Or a variety of LCP accelerating agents.Therefore, in some embodiments, first end may include one or more can be used for making it is a kind of or The aperture of the internal flow unicom of a variety of reacting precursor sources and reactor.For example, in some embodiments, reactor First end may include that one or more can be with aperture associated with the various source containers (such as passing through pipeline) comprising reacting precursor. In some embodiments, the first end of reactor may include that one or more can be with air source (such as containing CO₂Air source) connection To make that the aperture in reactor can be introduced a gas into.

When in use, the aperture in the first end of reactor can be used for controlling inside of the various reacting precursors to reactor Introducing, and therefore can be used for controlling the total rate of successive reaction carried out in the reactor.For example, in some implementations In scheme, the first end of reactor may include that the amount for being introduced into each reacting precursor in reactor can be configured to control, or can The various control elements (such as valve, metering device etc.) of the rate of inside for controlling each reacting precursor introducing reactor.Cause This, can be controlled in the input rate of each reacting precursor of the first end of reactor, and therefore can be used for controlling in reactor Kinetics.

The second end of reactor is configured to export one or more reaction products, such as BRP compositions and non-BRP Composition.Therefore, in certain embodiments, the second end of reactor may include that one or more can be used for autoreactor shifting Except the aperture of one or more reaction products.For example, in some embodiments, may include can for the second end of reactor The aperture of BRP compositions is removed for the inside of autoreactor.In some embodiments, the second end of reactor include can Inside for autoreactor removes the aperture of non-BRP compositions.

As above described in the first end about reactor, the aperture in the second end of reactor may include for example can be used for The given reaction product that autoreactor removes specified amount is controlled, or control autoreactor removes the control for the rate for giving reaction product Element processed.Therefore, it is can be controlled in the output speed of each reaction product of the second end of reactor, and therefore can be used for controlling Kinetics in reactor.In some embodiments, the aperture in the second end of reactor can with such as one or Multiple container fluid communications for being configured to receive reaction product.

In some embodiments, the different zones of the second end of autoreactor remove differential responses product.Citing comes It says, in some embodiments, the central part of the second end of autoreactor removes BRP compositions, and the of autoreactor The peripheral portion of two ends removes non-BRP compositions.Therefore, in certain embodiments, the second end of reactor may include To remove multiple apertures of these differential responses components in the different zones of the second end of reactor.For example, In some embodiments, the second end of reactor may include that the periphery of one or more second ends around reactor is fixed Position, and it is used for the aperture that autoreactor removes non-BRP compositions.The second end of reactor may also comprise one or more positions At or near the center of the second end of reactor, and for the aperture of autoreactor removal BRP compositions.Reactor The space orientation in the aperture in second end and interval contribute to autoreactor to remove differential responses product respectively.

In some embodiments, BRP reactors include be configured to facilitate one or more ion autoreactors One regioselectivity is transported to the selective ion separator of the second area of reactor.In this way, selective ion point It can for example be used to detach non-wanted ion from the BRP compositions generated in the reactor from device.

In some embodiments, the ion separator based on charge can be placed in positioned inside reactor, and by with Set in the holding structure to keep the ion separator based on charge or on.In some embodiments, holding structure is located at anti- Near the inner surface for answering the outer wall of device.In some embodiments, the inner surface of the outer wall of holding structure autoreactor is to reaction The center of device extends, and the guarantor between the outer surface of the inner wall of the inner surface and holding structure of the outer wall with defined reaction device Hold the inner wall in space.In certain embodiments, the inner wall of holding structure includes large pore material layer, such as diameter macropores film, It allows fluid and molecule passes freely through the film, while the ion separator based on charge being maintained at and is kept in space.? In the embodiment, the content of reactor can pass freely through the inner wall of holding structure with the ion separator based on charge Interaction.Holding structure can be built by any of a variety of suitable materials.It includes but not limited to gold to be suitble to the example of material Belong to and metal alloy (such as stainless steel, low-carbon alloy steel), ceramics, glass, aggregation group are graded.

In some embodiments, holding structure can be separated with reactor, be may be, for example, and be can be placed in inside reactor Independent structure.In the embodiment described in which, holding structure and reactor usually have same shape, and the size of holding structure It is such that holding structure can be placed on inside reactor.In some embodiments, holding structure can be placed on instead It answers inside device, and reactor can be movably attached to.

The many different variables of the scale visual of holding structure and change, the variable such as BRP generates scale, used anti- Answer condition, the operation mode (batch produces or continuous production) of reactor, the type etc. of the ion separator used based on charge. Therefore, keep the ratio of the cross-sectional area in space and the cross-sectional area of reactor can be from about 1:100 to about 1:50, to about 1:25, To about 1:20, to about 1:15, to about 1:10, to about 1:5, to about 1:4, to about 1:3, to about 1:2 variations.

In some embodiments, selective membrane may include size at about 1 angstrom (Angstrom) until about 10 angstroms, until about 20 angstroms, until about 30 angstroms, until about 40 angstroms, until about 50 angstroms, until about 60 angstroms, until about 70 angstroms, until about 80 angstroms, until about 90 angstroms, until about 100 angstroms, until about 200 angstroms, until about 300 angstroms, until about 400 angstroms, until about 500 angstroms, until about 600 angstroms, Up to about 700 angstroms, until about 800 angstroms, the hole in the range of about 900 angstroms or bigger.In the embodiment described in which, film transports It not only by the close dimensional limit of fenestra, but also is controlled by other transport phenomenas, the phenomenon includes such as surface charge Influence, the double-deck formation, Donnan balance (Donnan equilibrium), electrically charged substance relative mobility etc..

In some embodiments, selective membrane may include with size at about 5 angstroms until about 6 angstroms, until about 7 angstroms, it is straight The reverse osmosis membrane in the hole in the range of to about 8 angstroms.The film can not usually be permeated by ion, but hydrone is allowed to pass through film.

In some embodiments, reacting precursor can be introduced into the first area of the reactor divided, so that precursor is deposited It is on the first side of the ion separator based on size.Because precursor inside reactor react, based on size from Molecular separator can be used for the various reactive components of Selective Separation.For example, in some embodiments, the non-BRP groups of reaction Point can be transported through by selectivity or across the ion separator based on size, and BRP components can be retained in based on size from On first side of molecular separator.

In some embodiments, reactor includes that can be used for pressurizeing at least part of the inside of reactor so that anti- The pressure that the pressurized part of device has is answered to be more than the pressure-applying unit of the pressure of reactor external environment.The operating pressure model of reactor Enclosing for example can generate the size of scale and/or reactor based on required BRP and change, and can be usually in about 50psi until about 75psi, until about 100psi, until about 125psi, until about 150psi, until about 175psi, until about 200psi, until about 225psi, until about 250psi, including until in the range of about 500psi or higher.In some embodiments, in reactor The pressure in portion can in about 5atm until about 6atm, until about 7atm, until about 8atm, until about 9atm, until about 10atm, straight To about 11atm, until about 12atm, until about 13atm, until about 14atm, until in the range of about 15atm or higher.

In some embodiments, pressure-applying unit can be used for across the selective ion isolation for being placed on inside reactor Device applies pressure.For example, in some embodiments, including the selective ion separator of film can be placed in reactor Portion by reactor to be divided at least two different zones, and pressure-applying unit can be used for cross-film and apply pressure difference.In some implementations In scheme, that such as pressurizes contains CO₂ ^-Gas gas-pressurized can be used for cross-film apply pressure difference.

In some embodiments, BRP generations reactor may include multiple classifications as described above (as example such as Fig. 6 and 7 The first order of middle explanation and the second level), wherein individual reactors are connected in series, and communication each other.When in use, First reaction can carry out in the first stage, and can make the subsequent classification of one or more products arrival reactor of the first reaction To carry out other processing.It in some embodiments, can be before each individual classifications being connected in series with introduce one or more reactions Body substance.For example, other aqueous mediums or LCP accelerating agents can be introduced in first end at different levels.Therefore, reaction at different levels Product can further be refined by passing through multiple individual reactor classifications, such as to remove non-BRP reaction products, or further Make the reaction of BRP reaction products to generate higher carbon acid hydrogen radical yield.

In certain embodiments, the classification of connection can respectively be configured to carry out the aitiogenic different steps of BRP.It lifts For example, in some embodiments, the classification of two or more connections can have different sizes, and/or may include difference Component, such as different ions separator, such as different ions exchanger resin and/or different selective membrane, such as with different holes The film of size.In some embodiments, the classification of two or more connections can be identical.In certain embodiments, Two or more classifications can be connected in parallel, and product at different levels can be then in the feed-in third level to carry out other processing.? In the embodiment, at different levels is identical, or one or more classifications can be different.In a variety of suitable hierarchical compositions Any one can be used for generating theme BRP compositions.

The number for the classification that can be connected and/or be connected in parallel can 2 or more until 3 or more, until 4 or more, it is straight To 5 or more, until 10 or more, until 20 or more, until 30 or more, until 40 or more or until 50 or more In the range of.

Goal response device can include many other components as needed.For example, BRP reactors may include can be used for controlling The process control equipment of the aitiogenic various aspects of BRP processed, such as temperature control system and/or pH control systems.Citing For, in some embodiments, including heating component (such as temperature blanket), temperature probe and including temperature controller and place The temperature control system for managing the temperature control automation system of device can be used for maintaining the temperature of the content of BRP generation reactors to exist In specified for temperature ranges.For example, in some embodiments, temperature control system can be used for maintaining the interior of BRP reactors Inclusion be 35-40 DEG C in the range of at a temperature of.In some embodiments, temperature control system can be used for that BRP is made to react The temperature of the content of device is from the first temperature inversion to second temperature.For example, in some embodiments, temperature can maintain Continued for the first period at 35-40 DEG C, is then converted into 25-30 DEG C of range and continued for the second period.In some cases, it can wrap Ion selective electrode is included for example to provide the ability of monitoring salinity variation.

In some embodiments, it including acid source and alkali source, pH probes and is controlled including the pH of pH controllers and processor The pH for the content that the pH control systems of automated system can be used for that BRP is maintained to generate reactor is within the scope of specified pH.Citing For, in some embodiments, pH control systems can be used for that the content of BRP reactors is maintained to be 8.0 to 9.0pH units In the range of pH under.In some embodiments, pH control systems can be used for making the pH of the content of BRP reactors from first PH value is converted into the second pH value.For example, in some embodiments, pH can maintain 8.0 to continuing under 9.0pH units One period was then converted into 9.0 to the ranges of 10.0pH units and continued for the second period.

As outlined above, BRP reactors can be a part for the system for including other functional units.For example, BRP is anti- Answer device operationally can generate reactor combination with carbonate mine substance for example as described above.BRP reactors also can be with CO₂Production Raw device, such as industrial plant as described above combination.

Other system features

System may be present in land or sea.For example, system can be in coastal region, such as close to source of seawater, or Even in the system land based of inland locations, wherein water is from saline source (such as ocean) by pipeline to system. Alternatively, the system that system may be based on water, that is, the system being present in waterborne or water.The system can be present in as needed On ship, platform based on ocean etc..In certain embodiments, system can be in office with industrial plant (such as power plant) common location What suitable location.

Following embodiment is provided by way of illustration and not by way of limitation.

Experiment

I. the product rich in bicarbonate radical is generated with flow reactor

We use CO₂Make originally water saturation, and by both R.O. membrane filters and NF membrane filters come separation component. The key component of tap water is in this measurement.It is believed that the presence of ion helps to retain HCO during membrane filtration processes₃ ^-With And remove CO from retentate₂.It is unfavorable by using solion (even if dilute solution used herein) in membrane filtration processes Acid poisoning component can from retentate remove with generate have be more suitable for CaCO₃The product of the basicity of precipitated chemical.

We are detached using AD seawater R.O elements and An NF membranes respectively.Temperature during membrane filtration is 25 DEG C and 30 DEG C between.We test 400,600 and 800psi Δ P transmembrane pressures using pump.It is observed that (being worn in penetrant Cross the substance of filter) generate big pH gradient between retentate (despite the presence of filter, but the substance retained in flowing). The acidic components of this display solution are filtered out from retentate to enter in penetrant by means of R.O. and N.F. filters.

Fig. 9 provides the schematic diagram of R.O. reactors.As shown in Figure 9, as pump pressure (Δ P) increases, retentate is always And it is more more more alkaline than penetrant.Several in parallel and/or series connection R.O. films can be used for increasing the pH of retentate to contribute to CO₂ Isolation processes.For each condition (400,600,800psi), triplicate (n=3) collects data.

Figure 10 provides the schematic diagram of N.F. reactors.As pump pressure (Δ P) increases, retentate is always and more than infiltration Object is more alkaline.About the acidic components for removing retentate, the performance of N.F. films is not so good as R.O. films, but since it being capable of same time shift Except certain undesirable ions, so still can be helpful extremely to have.For each condition (400,600,800psi), one Three parts of collection data of formula.

Figure 11 is provided under various pump pressures (Δ P), the proton removed from retentate by penetrant during membrane filtration Score (in percentage), as calculated by pH and flow velocity.R.O. filter extremely efficiently removes acidic components from solution, from And it generates and is more suitable for CaCO₃The retentate of precipitation.NF membrane filters are successful in lesser degree, but are contributed to simultaneously certainly Our solution removal is non-to want " onlooker's ion ", such as Na⁺And Cl^-.The efficiency that proton is removed from retentate increases with (Δ P) And increase, this is the principle that can be used as needed.The width of error bar is two standard deviations, as surveyed at N=3 Amount.

Above scheme generation is characterized in that there are the products rich in bicarbonate radical of liquid condensation phase (LCP) droplet.LCP is small Drop is rich in Ca²⁺And bicarbonate ion, to generate LCP hard water characteristics.With can to handle strategy as the policy class of hard water For operating LCP.Addition or removal NaCl (aqueous solution) are that one kind can be easy to reach by using R.O., NF and UF filter The strategy.Addition NaCl can also be used for process water addition " softness " to operate LCP.It is small to can be used for handling " hard water " LCP Another technology for handling hard water of drop is addition additive, such as polymerization or proteins additive, such as poly-aspartate (ginseng See Gower etc. and other documents).These additives include polyaminoacid, sugar, protein, surfactant, micella and lipid Body.These additive positively chargeables or negatively charged, they can be hydrophilic or hydrophobic (or even amphiphilic).

II.BRP admixtures

Embodiment A：CO is prepared from high early strength (c-type, E types) super plasticity (A types, F types) business admixture₂Isolation Cement additive

CO₂Isolation cement additive A1 is with mainly by polycarboxylate (15-40wt%), sodium sulfocyanate (15- 40wt%), N, N, N ', the quotient that N '-four (2- ethoxys) ethylenediamine (5-10wt%), triethanolamine (1-5wt%) and water form It is prepared by industry admixture.The admixture of concentration is diluted to proper volume (such as 0.02L admixtures are in 1.0L water) with aqueous medium To obtain the dilution for the recommendation for being suitable for generating condensable cement composition.Then it will contain CO₂ ^-Gas be dissolved into solution To form BRLCP components, the amount of the inorganic carbon wherein dissolved in solution (DIC) is quantitative with UIC CM150 series carbon analyzers. Overview of the data is in Figure 12 and table 1.For this embodiment, contain CO compared to unused₂ ^-Gas treatment A1 control, with containing CO₂ ^-Gas treatment after, A1 show DIC increase by 650%.

After forming BRLCP components, CO can be made₂Isolation cement additive is combined to produce condensable with appropriate cement Cement composition (such as per 100kg cement 0.3-1.0L A1).

Embodiment B：CO is prepared from diminishing accelerator (c-type, E types) business admixture₂Isolation cement additive

CO₂Isolation cement additive A2 be with mainly by calcium nitrate (15-40w%), sodium sulfocyanate (10-30wt%), It is prepared by the business admixture of diethanol amine (10-30wt%), triethanolamine (3-7wt%) and water composition.The admixture of concentration is used Aqueous medium is diluted to proper volume (such as 0.06L admixtures are in 1.0L water) and is suitable for generating condensable cement group to obtain Close the dilution of the recommendation of object.Then it will contain CO₂Gas be dissolved into solution to form BRLCP components, wherein in solution The amount of DIC is quantitative with UIC CM150 series carbon analyzers.Overview of the data is in Figure 12 and table 1.For this embodiment, phase Contain CO compared with unused₂Gas treatment A2 control, with containing CO₂Gas treatment after, A2 show DIC increase by 2,670%. With CO is isolated in the form of BRLCP₂CO₂Isolation cement additive A1 is on the contrary, CO₂A2 is with solids for isolation cement additive CO is isolated in matter form₂Or its at least part.Referring also to following example D.

Table 1：

Embodiment C：Use CO₂Isolation cement additive prepares mortar cube

Mortar cube is by ratio (such as per the kg mortar 0.138L A1) mixed mortar and CO with 0.138 part₂Every It is prepared from property cement additive with attempting to follow ASTM C109 standards.Control cube is before being mixed with mortar, mixed Conjunction is not yet exposed to containing CO₂ ^-Gas underwater preparation.3 days cubical to a series of mortars prepared in this embodiment It is shown in Figure 13 with strength test in 7 days.For each group cube, by with CO₂Isolation cement additive is mixed with Cube shows that 3 days, test in 7 days and 28 days compressive strengths for testing the two are higher.Such as can in the result seen in, higher compression Intensity is with including CO₂The admixture of isolation component is reached.

Embodiment D：From CO₂The solution of isolation cement additive prepares solid carbonate material

Solid carbonate material is to contain CO by addition₂Gas to the concentration homogeneous solution of business admixture in prepare, institute Admixture is stated mainly by calcium nitrate (15-40w%), sodium sulfocyanate (10-30wt%), diethanol amine (10-30wt%), three ethyl alcohol Amine (3-7wt%) and water composition (such as the CO described in embodiment B₂Isolation cement additive A2).

Contain CO in addition₂Gas before, the pH of admixture solution is 10.5.Containing CO₂Gas be continuously to erupt shape Addition is to form BRLCP components (such as in such as embodiment B) in the case where pressure is less than 200psi (being less than 14atm) for formula, so that solution PH become pH 9.2 (after primary eruption), pH 8.3 (after two-stage eruption) and pH 4.9 (more than erupting three times Later), so as to cause forming dense slurries together.

Remaining liq admixture, which is removed, by decantation detaches solid matter from dense slurries.Solid matter is rinsed with water more It is secondary, decantation removal liquid after being rinsed at each time, and place in an oven to be dried.

Two tests confirm that dry separation solid is actually calcium carbonate：(i) it adds in 1.2M hydrochloric acid to solid matter Cause acutely to blister and (ii) X-ray diffraction (XRD) analysis instruction solid matter is calcite, pattern is shown in Figure 14 In.

Embodiment E：Prepare the CO for including MDEA and L-arginine₂Isolation cement additive

CO₂Isolation cement additive is prepared by combining 1wt%MDEA and 4wt%L- arginine.These components Account for CO₂The 5wt% of isolation cement additive, and it can be incorporated to 1.38wt%CO in the solution₂。CO₂Isolation cement adds Agent be using be dissolved in the aqueous medium (such as water) of proper volume with generate 36 gallons of final volume these components generate. Then it will contain CO₂Gas be dissolved into solution.The CO of dissolving₂It is reacted with MDEA and L-arginine to form BRLCP components, and And 1.38wt%CO₂It is incorporated into BRLCP components.After forming BRLCP components, CO can be made₂Isolation cement additive with it is suitable Cement composition is measured to generate condensable cement composition.As one gallon of this CO₂Isolation cement additive and appropriate cement and When another coagulating fluid (such as 35 gallons waters) is combined to produce one yard of condensable cement composition, the condensable cement composition 0.12lb CO are isolated in object₂.As 36 gallons of this CO₂Isolation cement additive is combined to produce one yard of condensable with appropriate cement When cement composition, the condensable cement composition isolation 4.17lb CO₂.This CO₂The composition of isolation cement additive It is summarized in table 2.

Table 2：

Embodiment F：Prepare the CO comprising TEOA, L-arginine and choline chloride₂Isolation cement additive

CO₂Isolation cement additive be by combine 8wt% triethanolamines (TEOA), 12wt%L- arginine and It is prepared by 5wt% choline chlorides.These components account for CO₂The 25wt% of isolation cement additive, and can in the solution simultaneously Enter 6.97wt%CO₂。CO₂Isolation cement additive is using being dissolved in the aqueous medium (such as water) of proper volume to produce These components of raw 36 gallons of final volume generate.Then it will contain CO₂Gas be dissolved into solution.The CO of dissolving₂With TEOA, L-arginine and choline chloride reaction are to form BRLCP components, and 6.97wt%CO₂It is incorporated into BRLCP components.It is being formed After BRLCP components, CO can be made₂Isolation cement additive is combined to produce condensable cement composition with appropriate cement.When One gallon of this CO₂Isolation cement additive is combined to produce with appropriate cement and another coagulating fluid (such as 35 gallons waters) When one yard of condensable cement composition, the condensable cement composition isolation 0.59lb CO₂.As 36 gallons of this CO₂Isolation Property cement additive and appropriate cement when being combined to produce one yard of condensable cement composition, the condensable cement composition every From 21.1lb CO₂.This CO₂The composition of isolation cement additive is summarized in table 3.

Table 3：

Embodiment G：Prepare the CO for including DEA, TEOA and L-arginine₂Isolation cement additive

CO₂Isolation cement additive be by combine 7wt% triethanolamines (TEOA), 8wt%L- arginine and It is prepared by 10wt% diethanol amine (DEA).These components account for CO₂The 25wt% of isolation cement additive, and can be molten 6.18wt%CO is incorporated in liquid₂。CO₂Isolation cement additive is using the aqueous medium (such as water) for being dissolved in proper volume In with generate 36 gallons of final volume these components generate.Then it will contain CO₂Gas be dissolved into solution.The CO of dissolving₂ It is reacted with TEOA, L-arginine and DEA to form BRLCP components, and 6.18wt%CO₂It is incorporated into BRLCP components.In shape After BRLCP components, CO can be made₂Isolation cement additive is combined to produce condensable cement composition with appropriate cement. As one gallon of this CO₂Isolation cement additive is combined with appropriate cement and another coagulating fluid (such as 35 gallons waters) to produce When raw one yard of condensable cement composition, the condensable cement composition isolation 0.52lb CO₂.As 36 gallons of this CO₂Every When being combined to produce one yard of condensable cement composition from property cement additive and appropriate cement, the condensable cement composition 18.7lb CO are isolated₂.This CO₂The composition of isolation cement additive is summarized in table 4.

Table 4：

Embodiment H：Prepare the CO comprising THEED, Tysol SM, TEOA acetates and choline chloride₂Isolation cement adds Add agent

CO₂Isolation cement additive is by combining 5wt%THEED, 10wt%Tysol SM, 30wt%TEOA acetic acid It is prepared by salt and 30wt% choline chlorides.These components account for CO₂The 75wt% of isolation cement additive, and can be in solution In be incorporated to 18.4wt%CO₂。CO₂Isolation cement additive is to use to be dissolved in the aqueous medium (such as water) of proper volume These components to generate 36 gallons of final volume generate.Then it will contain CO₂Gas be dissolved into solution.The CO of dissolving₂With THEED, Tysol SM, TEOA and choline chloride reaction are to form BRLCP components.Due to CO₂Reacting between tertiary amine is slower Property, by solution storage between 2 to 5 days, one between 1 to 7 week or between 2 to 4 months Section period is so that the CO dissolved₂It reacts, is then reacted with amine to form BRLCP components with water.

After forming BRLCP components, CO can be made₂Isolation cement additive is combined to produce condensable with appropriate cement Cement composition.As one gallon of this CO₂Isolation cement additive and appropriate cement and another coagulating fluid (such as 35 gallons Water) when being combined to produce one yard of condensable cement composition, the condensable cement composition isolation 1.54lb CO₂.When 36 plus This CO of logical sequence₂It is described to coagulate when isolation cement additive is combined to produce one yard of condensable cement composition with appropriate cement Tie cement composition isolation 55.6lb CO₂.This CO₂The composition of isolation cement additive is summarized in table 5.

Table 5：

Embodiment I：Prepare the CO comprising MDEA, choline chloride and ammonium chloride and rice hull ash₂Isolation cement additive

CO₂Isolation cement additive be by combine 10wt%MDEA, 10wt% choline chloride and 5wt% ammonium chlorides come It prepares.These components account for CO₂The 25wt% of isolation cement additive, and it can be incorporated to 10.9wt%CO in the solution₂.It will Rice hull ash (i.e. a kind of mainly volcanic ash from being formed in the pure silicon dioxide of non-crystalline forms) is suspended in solution with to mixing Object provides thermostabilization.CO₂Isolation cement additive be using be dissolved in the aqueous medium (such as water) of proper volume with These components for generating 36 gallons of final volume generate.Then it will contain CO₂Gas be dissolved into solution.The CO of dissolving₂With MDEA, choline chloride and ammonium chloride reaction are to form BRLCP components, and 10.9wt%CO₂It is incorporated into BRLCP components.? It is formed after BRLCP components, CO can be made₂Isolation cement additive is combined to produce condensable cement composition with appropriate cement Object.As one gallon of this CO₂Isolation cement additive is combined with appropriate cement and another coagulating fluid (such as 35 gallons waters) When generating one yard of condensable cement composition, the condensable cement composition isolation 0.92lb CO₂.When 36 gallons this CO₂When isolation cement additive is combined to produce one yard of condensable cement composition with appropriate cement, the condensable cement 33.1lb CO are isolated in composition₂.This CO₂The composition of isolation cement additive is summarized in table 6.

Table 6：

Although system above is described for component part, system can be configured to carry out batch or continuous anti- It answers, such as above described in method chapters and sections.For example, system can be configured to carry out the batch reaction embodiment party of method Case, such as the product rich in bicarbonate radical is wherein generated in the first reactor, it is then subjected to precipitation item in the second reactor Part.Alternatively, system can be configured to perform the continuous embodiment of method, such as wherein in the first part of single-reactor The product rich in bicarbonate radical is generated, is then subjected to deposition condition in the second part of same reactor as described above.

Embodiment III.

As 0.2mM CaCl₂, and with wherein there is CO in the saline solution of the simulation containing 4 milliequivalent basicity₂Simulation Flue gas inflate with reach saturation.At this point, the pH of the saline solution of saturation is pH 5.30.Make solution under 400psi pressure Across reverse osmosis (R.O.) filter cell repeatedly to remove acidic components from solution.After being passed through twice with four times, use NS500 nano-particle tracking analyser analytical solutions are to detect liquid condensation phase in product (BRP) of the gained rich in bicarbonate radical (LCP) existence of droplet.After passing twice through, pH value of solution has been increased to numerical value 6.8, and detects LCP droplets.It measures The size of droplet and the zeta potential of droplet, and result is shown in Figure 15 A and Figure 15 B.Numerical value with about with NaHCO₃Salt The size of the LCP droplets of preparation is consistent with the numerical value that zeta potential obtains.After so that solution is passed through R.O. units four times, solution PH increases to numerical value 7.3, and CaCl₂And HCO₃ ^-It is concentrated, this results in crystalline material, special based on the scattering observed Property, the crystalline material is solid CaCO₃。

Although having appended claims, the disclosure is also by following definition of term：

1. a kind of self-contained CO₂Gas remove carbon dioxide (CO₂) method, the method includes：

The gas and aqueous medium is set to contact being enough the under conditions of of generating the product rich in bicarbonate radical；

To contain CO from described₂Gas remove CO₂。

2. the method as described in clause 1, wherein the aqueous medium is the aqueous medium of buffered with bicarbonate.

3. the method as described in clause 2, wherein the aqueous medium of the buffered with bicarbonate has in the range of 8 to 10 PH.

4. the method as described in clause 1,2 or 3, wherein containing CO described in being contacted with the aqueous medium of buffered with bicarbonate₂ Gas pCO₂It is 10⁴Pa or higher.

5. the method as described in any one of aforementioned clause, wherein the product rich in bicarbonate radical includes solidifying containing liquid The bulk liquid of the droplet of rephasing (LCP).

6. the method as described in any one of aforementioned clause, wherein making described containing CO₂Gas and the aqueous medium exist Mediate CO₂It is converted in the presence of the catalyst of bicarbonate radical and contacts.

7. the method as described in clause 6, wherein the catalyst is enzyme.

8. the method as described in clause 7, wherein the enzyme is carbonic anhydrase.

9. the method as described in clause 6, wherein the catalyst is synthetic catalyst.

10. the method as described in clause 6, wherein the catalyst is metal colloid particles catalyst.

11. the method as described in any one of aforementioned clause, wherein making described containing CO₂Gas and the aqueous medium exist It is contacted in the presence of silica source.

12. the method as described in any one of aforementioned clause, wherein making described containing CO₂Gas and the aqueous medium exist It is contacted in the presence of LCP accelerating agents.

13. the method as described in any one of aforementioned clause further includes being enough to generate solid carbonic acid salt composite Under the conditions of combine the product rich in bicarbonate radical or its component and cationic source.

14. the method as described in clause 13, wherein the cationic source is bivalent cation source.

15. the method as described in clause 14, wherein the bivalent cation is alkaline earth metal cation.

16. the method as described in clause 15, wherein the divalent alkaline-earth metal cation is selected from Ca²⁺And Mg²⁺And its group It closes.

17. the method as described in any one of clause 13 to 16, wherein the solid carbonate composition be without using It is generated under source of alkalinity.

18. the method as described in any one of clause 13 to 17, wherein the method further include from the solid carbonate Composition generates commodity.

19. the method as described in clause 18, wherein the commodity are construction materials.

20. the method as described in clause 19, wherein the construction material is aggregate.

21. the method as described in clause 19, wherein the construction material is cement or complementarity cement material.

22. the method as described in any one of clause 1 to 12, wherein the method includes storing the richness after a birth One period of product containing bicarbonate radical.

23. the method as described in any one of clause 1 to 12, wherein described rich in bicarbonate radical the method includes combining Product and hydraulic cement.

24. the method as described in any one of clause 1 to 12, wherein described rich in bicarbonate radical the method includes combining Product and chemical admixture.

25. the method as described in any one of clause 5 to 24, wherein bicarbonate anion in the LCP droplets Concentration is 10,000ppm or higher.

26. the method as described in any one of clause 5 to 25, wherein bicarbonate anion in the LCP droplets with The molar ratio of carbonate anion be 10 or bigger than 1.

27. the method as described in any one of aforementioned clause, wherein the reaction is successive reaction.

28. the method as described in any one of aforementioned clause, wherein the reaction is batch reaction.

29. the method as described in any one of aforementioned clause, wherein the method are isolation CO₂Method.

30. the method as described in any one of aforementioned clause, wherein the method are for removed from gas stream every 2 moles CO₂, generate the CO of 1 mole of purifying₂With by dilute flue gas be converted to concentration close to pure CO₂Logistics.

31. the method as described in any one of aforementioned clause, wherein described contain CO₂Gas be from industrial plant obtain.

32. one kind being used for self-contained CO₂Gas remove CO₂System, the system comprises：

It is described to contain CO₂The source of gas；

Aqueous medium source；With

It is configured to make described containing CO₂Gas and the aqueous medium be enough to generate the product rich in bicarbonate radical Under the conditions of the reactor that contacts.

33. the system as described in clause 32, wherein the reactor includes mediating CO₂It is converted to the catalysis of bicarbonate radical Agent.

34. the system as described in any one of clause 32 to 33, wherein described contain CO₂The source of gas be industrial work Factory.

35. the system as described in clause 34, wherein described contain CO₂The source of gas be flue gas.

36. the system as described in clause 35 is started wherein the industrial plant is power plant, cement plant or Modular gas Machine (or you want any engine for being known as watt Ceylon (Wartsila) engine).

37. the system as described in any one of clause 32 to 36, wherein the aqueous medium is underground water, seawater or salt Water.

38. the system as described in any one of clause 32 to 37, wherein the system is configured to be rich in carbonic acid from described The product of hydrogen radical generates solid carbonic acid salt composite.

39. the system as described in any one of clause 32 to 38, wherein the system does not include source of alkalinity.

40. the system as described in any one of clause 32 to 39, wherein the system is and industrial plant common location.

41. a kind of method generating the product (BRP) rich in bicarbonate radical, the method includes：

It is combined under conditions of being enough to generate BRP：

Carbon dioxide (CO₂) source；

Water phase；With

Liquid condensation phase (LCP) accelerating agent；

It is generated in reactor in continuous BRP；And

Reactor, which is generated, from the BRLCP obtains the BRP compositions.

42. the method as described in clause 41, wherein the LCP accelerating agents include LCP promotion property cations.

43. the method as described in clause 42, wherein LCP promotion property cations include divalent alkaline-earth metal cation.

44. the method as described in clause 43, wherein the divalent alkaline-earth metal cation is selected from Ca²⁺And Mg²⁺And its group It closes.

45. the method as described in any one of clause 41 to 44, wherein the LCP accelerating agents further include pair anion.

46. the method as described in any one of clause 41 to 45 is configured to export wherein the BRP generates reactor BRP compositions and non-BRP compositions.

47. the method as described in clause 46, wherein the BRP compositions include LCP promotion property cations, and it is described Non- BRP compositions include the pair anion.

48. the method as described in any one of clause 45 to 47, wherein the pair anion is Cl^-。

49. the method as described in any one of clause 45 to 48 is configured to wherein the BRP generates reactor described in Pair anion described in BRP composition Selective Separations.

50. the method as described in clause 49 is configured to wherein the BRP generates reactor from BRP compositions electricity Detach the pair anion.

51. the method as described in clause 49 is configured to wherein the BRP generates reactor from the BRP compositions ruler The very little separation pair anion.

52. the method as described in clause 51, wherein it includes the choosing that the pair anion may pass through that the BRP, which generates reactor, Selecting property film.

53. the method as described in clause 52, wherein the film is size selectivity film.

54. the method as described in any one of aforementioned clause, wherein combining the carbon dioxide (CO under stress₂) source； The water phase；With liquid condensation phase (LCP) accelerating agent.

55. the method as described in clause 52, wherein combining the dioxy under the pressure being in the range of 50 to 1000psi Change carbon (CO₂) source；The water phase；With liquid condensation phase (LCP) accelerating agent.

56. the method as described in any one of clause 41 to 55, wherein the BRP reactors are single-stage reactors.

57. the method as described in any one of clause 41 to 55, wherein the BRLCP reactors are to include at least first order With the multistage reactor of the second level.

58. the method as described in clause 57, wherein the process conditions in the first order and the second level are different.

59. the method as described in any one of clause 41 to 58, wherein the BRP include substantially seldom (if there is Words) chlorion.

60. the method as described in any one of clause 41 to 59, wherein the reactor includes being configured to from described anti- The content of device is answered to remove the cathode of H+.

61. a kind of continuous product (BRP) reactor for being rich in bicarbonate radical, the reactor include：

First end and second end, wherein the first end is configured to receive：

Carbon dioxide (CO₂) source；

Water phase；With

Liquid condensation phase (LCP) accelerating agent；And

The second end is configured to output BRP compositions.

62. the reactor as described in clause 61, wherein the reactor includes being configured to make BRP compositions and non-BRP The separator of composition separation.

63. the reactor as described in clause 62, wherein the separator includes the separator based on size.

64. the reactor as described in clause 63, wherein the separator based on size includes film.

65. the reactor as described in clause 64, wherein the film is NF membrane.

66. the reactor as described in clause 64, wherein the film is ultrafiltration membrane.

67. the reactor as described in any one of clause 61 to 66, wherein the reactor is single-stage reactor.

68. the reactor as described in any one of clause 61 to 66, wherein the reactor is multistage reactor.

69. the reactor as described in any one of clause 61 to 68, wherein the reactor includes tube-like envelope and inside Tubular film.

70. a kind of system comprising operationally with CO₂Reaction associated with source as described in any one of clause 61 to 69 Device.

71. the system as described in clause 70, wherein the CO₂Source includes industrial plant.

72. the system as described in any one of clause 70 or 71, wherein the reactor operationally with carbonate deposition Reactor is combined.

73. a kind of method generating cement composition, the method includes the groups in a manner of being enough to generate cement composition It closes：

Cement component；With

Product (BRP) rich in bicarbonate radical.

74. the method as described in clause 73, wherein the BRP is according to such as any one of clause 1 to 31 and 41 to 60 The composition that the method generates.

75. the method as described in any one of clause 73 to 74, wherein the bicarbonate additive is liquid.

76. the method as described in any one of clause 73 to 75, wherein the cement is hydraulic cement.

77. the method as described in clause 76, wherein the hydraulic cement is Portland cement.

78. the method as described in any clause 73 to 77, wherein the condensable cement composition also includes aggregate.

79. the method as described in any clause 73 to 77, wherein the condensable cement composition also includes non-bicarbonate Salt additives.

80. the method as described in clause 79, wherein the non-carbon acid hydrogen salt additive is chemical admixture selected from the following： Water reducing ability additive；The entrainment additive of air；Condense controlling additive；Retardancy additive；Acceleration additive；It can add Work additive；Corrosion-inhibiting additive；Shrink reduction property additive；Permeability modulability additive；Cold day air water mud Additive；Underwater cement additive；And combinations thereof.

81. the method as described in clause 80, wherein make before being combined with the cement component the chemical admixture with The BRP combinations.

82. the method as described in any one of clause 73 to 81, wherein the cement composition also includes flying dust, slag And/or one or more of pozzolanic components.

83. a kind of cement composition is generated according to the method as described in any one of clause 73 to 82.

84. a kind of method of manufacture structure, the method includes：

The condensable cement composition as described in clause 83 is set to be located in a certain place；And

The condensable cement composition is set to condense into solid product in the place.

85. a kind of liquid CO₂Isolation bicarbonate additive.

86. a kind of solid carbonic acid hydrogen salt additive is by the liquid carbonic acid hydrogen salt additive described in clause 85 freely Water is detached to generate.

87. a kind of generation CO₂The method of isolation cement admixture composition, the method includes：

To be enough to generate the CO₂The mode combinatorial chemistry admixture and CO of isolation cement admixture composition₂Source.

88. a kind of external member comprising：

Cement；With

Product (BRP) rich in bicarbonate radical.

89. the external member as described in clause 88, wherein the BRP is according to such as any one of clause 1 to 31 and 41 to 60 The composition that the method generates.

90. the external member as described in clause 88 or 89, wherein the external member further includes chemical admixture.

91. the external member as described in clause 90, wherein the chemistry admixture is combined with the BRP in the external member.

92. a kind of bicarbonate liquid has 10 or smaller δ¹⁸O (SMOW) value.

93. a kind of bicarbonate liquid, with negativity δ¹³C (PDB) value.

Although the aforementioned present invention is retouched for the clarity purpose of understanding by explanation and way of example in more detail It states, but it is that can be wanted not departing from accompanying right to be easy to apparent easy to know in view of religious doctrine of the invention for those of ordinary skill in the art Certain change and modification are carried out to the present invention under the spirit or scope asked.

Therefore, previously described only to illustrate the principle of the present invention.Although should be appreciated that those skilled in the art will design not It is expressly recited or shows herein, but embody the principle of the present invention, and include within the spirit and scope of the present invention each Kind arrangement.In addition, all examples and conditionity wording all main purposes described herein as assist the readers in understanding the principles of the invention It, to promote the concept contributed of this field, and is to be interpreted as being not limited to the example and item clearly described with by inventor Part.In addition, all statements of the principle of the present invention described herein as, aspect and embodiment and its specific example are both intended to cover Both its structural equivalents and functional equivalent.In addition, it is intended that the equivalent includes that currently known equivalent will be opened with future Both equivalents (any element unrelated with structure for the execution identical function developed) of hair.Therefore, the scope of the present invention It is not intended to be limited to exemplary implementation scheme shown and described herein.More precisely, scope and spirit of the present invention are to pass through Appended claims embody.

Claims

The gas is set to be contacted with the aqueous medium of buffered with bicarbonate to generate the product for being rich in bicarbonate radical；With

The combination product rich in bicarbonate radical or its component and cationic source are to generate solid carbonic acid salt composite, without making With other source of alkalinity；

To contain CO from described₂Gas remove CO₂, wherein the method is for every 2 moles of CO for being removed from gas stream₂, generate 1 Mole purifying CO₂；

The wherein described product rich in bicarbonate radical includes the bulk liquid of the droplet of phase containing liquid condensation.

2. the method as described in claim 1, wherein the aqueous medium has pH in the range of 8 to 10.

3. the method as described in claim 1, wherein making described containing CO₂Gas and the aqueous medium mediating CO₂It is converted to It is contacted in the presence of the catalyst of bicarbonate radical.

4. the method as described in claim 1, wherein making described containing CO₂Gas mutually promote in liquid condensation with the aqueous medium It is contacted in the presence of into agent.

5. the method as described in claim 1, wherein the cationic source is bivalent cation source.

6. method as claimed in claim 5, wherein the bivalent cation is alkaline earth metal cation.

7. method as claimed in claim 6, wherein the divalent alkaline-earth metal cation is selected from Ca²⁺And Mg²⁺And combinations thereof.

8. the method as described in claim 1, wherein the concentration of the bicarbonate anion in the liquid condensation phase droplet is 10,000ppm or higher.

9. the method as described in claim 1, wherein the bicarbonate anion in the liquid condensation phase droplet and carbonate The molar ratio of anion be 10 or bigger than 1.

10. the method as described in any one of claim 1 to 7, wherein the reaction is successive reaction.

11. the method as described in any one of claim 1 to 7, wherein the method are isolation CO₂Method.

12. the method as described in any one of claim 1 to 7, wherein the aqueous medium includes amine.